Perfluorinated amide salts and their uses as ionic conducting materials

ABSTRACT

The invention concerns ionic compounds in which the anionic load has been delocalized. A compound disclosed by the invention is comprised of an amide or one of its salts, including an anionic portion combined with at least one cationic portion M +m  in sufficient numbers to ensure overall electronic neutrality; the compound is further comprised of M as a hydroxonium, a nitrosonium NO + , an ammonium —NH 4 +, a metallic cation with the valence m, an organic cation with the valence m, or an organometallic cation with the valence m. The anionic portion matches the formula R F —SO x —N − Z, wherein R F  is a perfluorinated group, x is 1 or 2, and Z is an electroattractive substituent. The compounds can be used notably for ionic conducting materials, electronic conducting materials, colorants, and the catalysis of various chemical reactions.

[0001] The present invention relates to ionic compounds in which theanionic charge is delocalized, and there uses.

[0002] It is known and it is particularly interesting to introduce ionicgroups in molecules or organic polymers having various functions.Coulombic stresses correspond, indeed, to the stronger interactionswhich are available at the molecular level, and the ionic groups modifyin an utmost manner the molecules to which they are bonded. Coloringmatters which are made soluble in water by means of sulfonate orcarboxylate functions may be mentioned.

[0003] However, the groups of this types, —CO₂ ⁻ 1/mM^(m+) or —SO₃ ⁻1/mM^(m+), are not dissociated, and they do not induce solubility insolvents other than water or certain highly polar protic solvents suchas light alcohols, which considerably restrict the scope of theirutilization.

[0004] On the other hand, salts of the compounds [R_(F)SO₂—N—SO₂R_(F)]1/mM^(m+) in which R_(F) is a perfluorinated group and M^(m+) is acation of valence m+ are known, which are soluble and are dissociated inorganic aprotic media or solvating polymers. It is however consideredthat the existence of two perfluoroalkylsulfonyl groups (in particularthe existence of fluorine atoms on the a atom of carbon of each sulfonylgroup) which exert an important attracting power on the electrons of theionic charge, is a necessary condition to obtaining properties ofsolubility and dissociation. For example, the pK_(a) of the acidH[CF₃SO₂—N—SO₂CF₃] is only 1.95, which compares to that of thenon-fluorinated acid CH₃SO₃H (pK_(a)=0.3) and is clearly inferior tothat of perfluorinated acid CF₃SO₃H (pK_(a)<−9) because of the basiccharacter of the central nitrogen atom with respect to the oxygen atomof sulfonic acids.

[0005] Surprisingly, the inventors have found that the excellentproperties of solubility and dissociation of the ionic groups—SO₂—N—SO₂— were maintained when a single sulfonated group has fluorineatoms on atoms which are adjacent to the sulfur atom, giving anextremely wide choice of functional molecules. In a manner also quiteunexpected, it has been noted that it was possible for obtaining thesame properties, to omit the group —SO₂ bound to the non-perfluorinatedgroup provided that the group which is directly bound to nitrogen has aHammett parameter σ* higher than 0.6. By way of comparison, the Hammettparameters σ* of a group —SO₂— bound to a non-perfluorinated group is3.5 and 4.55 for a group CF₃SO₂—.

[0006] The present inventors have also found that the sulfonyl —SO₂—groups could be replaced, with minor variations of properties, bysulfinyl —SO— or phosphonyl —PO=groups.

[0007] It is consequently an object of the present invention to providea family of ionic compounds having a good solubility and a gooddissociation, without having to rely on complex modifications of thestarting molecule. The precursors of the molecule of the invention arefound in the form of derivatives of sulfonic acids or of amine groups onthe one hand, and derivatives of perfluorosulfonyl types on the otherhand, which for the most part are industrial products and/or are easilyaccessible. In addition, it should be noted that a decrease of theperfluorinated fraction in the compounds of the invention enables toreduce the production costs of said compounds and consequently the costof the applications in which they are involved.

[0008] A compound of the present invention is an ionic compoundconsisting of an amide or one of its salts, comprising an ionic partassociated with at least a cationic part M^(m+) in sufficient number toensure an electronic neutrality to the assembly. It is characterized inthat M^(m+) is a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, ametallic cation having a valency m, an organic cation having a valencym, or an organo-metallic cation having a valency m, and in that theanionic part corresponds to the formula R_(F)—SO_(x)—N⁻Z, in which:

[0009] the group —SO_(x)— represents a sulfonyl group —SO₂— or asulfinyl group —SO—;

[0010] R_(F) is a halogen or a perhalogenated alkyl, alkylaryl,oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical correspondingto one of the formulae R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— orCF₃C(R_(A))F— in which R_(A)— represents a non-perhalogenated organicradial;

[0011] Z represents an electro-attractor radical having a Hammettparameter at least equal to that of a phenyl radical, and selected from:

[0012] j) —CN, —NO₂, —SCN, —N₃, —CF₃, R′_(F)CH₂— (R′_(F) being a pair offluorinated radicals, preferably CF₃—), fluoroalkyloxy radicals,fluoroalkylthioxy radicals,

[0013] jj) radicals comprising one or a plurality of aromatic nucleipossibly containing at least one nitrogen, oxygen, sulfur or phosphorusatom, said nuclei possibly being condensed nuclei and/or said nucleipossibly carrying at least one substitutent selected from halogens, —CN,—NO₂, —SCN, —N₃, —CF₃, CF₃CH₂—, CF₂═CF—O—, perfluoroalkyl groups,fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl,oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-allkenyl, thia-alkyl,thia-alkenyl groups, polymer radicals and radicals having at least onecationic ionophoric group and/or at least one anionic ionophoric group;

[0014] it being understood that a substituent Z may be a monovalentradical, part of a multivalent radical carrying a plurality of groupsR_(F)—SO_(x)—N—, or a segment of a polymer; or

[0015] Z is a radical R_(D)—Y— in which Y is a sulfonyl, sulfinyl orphosphonyl group and R_(D) is a radical selected from the groupconsisting of:

[0016] a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl oralkenylaryl radicals, alicyclic or heterocyclic radicals, includingpolycyclic radicals;

[0017] b) alkyl or alkenyl radicals comprising at least one functionalether, thioether, amine, mime, carboxyl, carbonyl, hydroxy, silyl,isocyanate or thioisocyanate functional group;

[0018] c) aryl, arylakyl, arylalkenyl, allylaryl or alkenylarylradicals, in which the aromatic nuclei and/or at least one substitutentof the nucleus comprises heteroatoms such as nitrogen, oxygen, sulfur;

[0019] d) radicals comprising condensed aromatic cycles which possiblycomprise at least one heteroatom selected from nitrogen, oxygen, sulfur;

[0020] e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl oralkenylaryl radicals in which the number of carbon atoms carrying atleast one halogen is at most equal to the number of non-halogenatedcarbon atoms, the α carbon of group Y not being halogenated when Y is—SO₂—, said radicals possibly comprising functional ether, thioether,amine, mime, carboxyl, carbonyl, hydroxy, silylalkyl, silylaryl,isocyanate or isothiocyanate groups;

[0021] f) radicals R_(c)C(R′) (R″)—O— in which R_(c) is a perfluorinatedalkyl radical and R′ and R″ are independently from one another anhydrogen atom or a radical such as defined in a), b), c) or d) above[for example CF₃CH₂O—, (CF₃)₃CO—, (CF₃)₂CHO—, CF₃ CH(C₆H₅)O—,—CH₂(CF₂)₂CH₂—];

[0022] g) radicals (RB)₂N—, in which the radicals R_(B) are identical ordifferent and are as defined in a), b), c), d) and e) above, one of theR_(B) could be an hydrogen atom or the two radicals R_(B) togetherforming a bivalent radical which constitutes a cycle with N;

[0023] h) radicals constituted by a polymer chain;

[0024] i) radicals having one or more cationic ionophoric groups and/orone or more anionic ionophoric groups;

[0025] it being understood that a substituent R_(D) could be amonovalent radical, part of a multivalent radical carrying a pluralityof groups R_(F)—SO_(x)—N—Y—, or a segment of a polymer;

[0026] it being understood that when Y is a sulfonyl and when R_(D) is aradical as defined in a), R_(F) is R_(A)CF₂—, R_(A)CF₂CF₂—,R_(A)CF₂CF(CF₃)—, CF₃C(R_(A))F— or a perhaloalkyl radical having 1 to 2carbon atoms not favouring a phase separation due to the aggregation ofthe fluorinated segments.

[0027] In a compound of the present invention, the cation may be ametallic cation selected from cations of alkali metals, cations ofalkali-earth metals, cations of transition metals, cations of tri-valentmetals, cations of a rare earth. By way of example, Na⁺, Li⁺, K⁺, Sm³⁺,La³⁺, Ho^(3+, Sc) ³⁺, Al³⁺, Y³⁺, Yb³⁺, Lu³⁺, Eu³⁺may be cited.

[0028] The cation may also be an organo-metallic cation, for example ametallocenium. By way of example, there may be mentioned the cationsderived from ferrocene, titanocene, zirconocene, indenocenium or ametalloceniurm arene, cations of transition metals complexed withligands of a phosphine type possibly having a chirality, organo-metalliccations having one or more alkyl or aryl groups co-valently fixed to anatom or a group of atoms, such as methylzinc, phenylmercury, trialkyltinor trialkyllead cations. The organo-metallic cations may be part of apolymer chain.

[0029] According to a variant of the invention, the compounds of theinvention have an organic cation selected from the group consisting ofR₃O⁺ (oxonium), NR₄ ⁺ (ammonium), RC(NHR₂)₂ ⁺ (amidiniurn), C(NHR₂)₃ ⁺(guanidinium), C₅R₆N⁺ (pyridinium), C₃R₅N₂ ⁺ (imidazolium), C₃R₇N₂ ⁺(imidazolinium), C₂R₄N₃ ⁺ (triazolium), SR₃ ⁺ (sulfonium), PR₄ ⁺(phosphonium), IR₂ ⁺ (iodonium), (C₆R₅)₃C+ (carbonium) cations. In agiven cation, the radicals R may all be identical. However, a cation mayalso include radicals R which are different from one another. A radicalR may be a H or it may be selected from the following radicals:

[0030] alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl,thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl,alkyl-aryl, alkenyl-aryl, dialkylamino and dialkylazo radicals;

[0031] cyclic or heterocyclic radicals possibly comprising at least onelateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;

[0032] cyclic or heterocyclic radicals possibly comprising heteroatomsin the aromatic nucleus;

[0033] groups comprising a plurality of aromatic or heterocyclic,condensed or non-condensed nuclei, possibly containing at least onenitrogen, oxygen, sulfur or phosphorus atom.

[0034] When an onium cation carries at least two radicals R which aredifferent from H, these radicals may constitute together a cycle whichis aromatic or non-aromatic, possibly enclosing the center carrying thecationic charge.

[0035] When the cationic part of a compound of the invention is an oniumcation, it may be either in the form of an independent cationic groupwhich is bound to the anionic part only by the ionic bond between thepositive charge of the cation and the negative charge of the anionicpart. In this case, the cationic part may be part of a recurring unit ofa polymer.

[0036] An onium cation may also be part of the radical Z or the radicalR_(D) carried by the anionic centre. In this case, a compound of theinvention constitutes a zwitterion.

[0037] When the cation of a compound of the invention is an oniumcation, it may be selected so that it can introduce into the compoundsubstituents permitting to confer specific properties to said compound.For example, the cation M⁺ may be a cationic heterocycle with aromaticcharacter, including at least one alkylated nitrogen atom in the cycle.By way of example, there may be cited an imidazolium, a triazolium, apyridinium, a 4-dimethylaniino-pyridinium, said cations possiblycarrying a substituent on the carbon atoms of the cycle. Among thesecations, those which give an ionic compound according to the inventionin which the melting point is lower than 150° C. are particularlypreferred. Such a compound having a low melting point is particularlyuseful for the preparation of materials with protonic conduction. Amaterial with protonic conduction which is particularly preferredcomprises a compound according to the invention in which the cation isformed by addition of a proton on the nitrogen of an imidazoline, animidazole or a triazole, as well as the nitrogenated corresponding basein a proportion of 0.5 to 10 in molar ratio.

[0038] A compound of the invention in which the cation M is a cationicgroup having a bond —N═N—, —N═N⁺, a sulfonium group, an iodonium group,or a substituted or non-substituted arene-ferrocenium cation, possiblyincorporated in a polymeric network, is interesting insofar as it can beactivated by a source of actinic energy of suitable wavelength.Particular examples of such compounds include those in which the cationis a diaryliodonium, dialkylaryliodonium, triarylsulfonium, trialkylarylsulfonium, or phenacyl-dialkyl sulfonium radical which is substituted ornon-substituted. The above cations may be part of a polymer chain.

[0039] The cation M of a compound of the invention may include a group2,2′[azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-azobis(2-amidiniopropane)²⁺. The compound of the invention is thencapable of releasing, under the action of heat or an ionizing radiation,radicals which enable initiation of polymerization, cross-linkingreactions or, in a general manner, chemical reactions involving freeradicals. Moreover, these compounds are easily soluble in polymeric andmonomeric organic solvents even of low polarity, contrary to thederivatives of anions of the type Cl⁻ normally associated with this typeof compounds. On the other hand, they have a negligible vapour pressurecontrary to the other radical initiators of the peroxide or azo type,which is a considerable advantage for the preparation of thin polymerfilms, the volatility of the initiator having as a consequence a badpolymerization or cross-linking of the surface of the film.

[0040] In an embodiment of the invention, R_(F) is a fluorine atom or apair of halogenated alkyl radicals preferably having from 1 to 12 carbonatoms, or a pair of halogenated alkylaryl radicals preferably havingfrom 6 to 9 carbon atoms. The pair of halogenated alkyl radicals may bea linear or branched radical. In particular, radicals in which thecarbon atom which will be in α position with respect to the group—SO_(x)— carries at least one fluorine atom, may be cited. Examples ofsuch radicals include R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— orCF₃C(R_(A))F— in which R_(A) represents a non-perhalogenated organicradical, an allyl group, an aryl group, an alkylaryl or arylalkcylgroup; a group comprising at least one ethylenic unsaturation and/or acondensable group and/or a dissociable group; a mesomorphous group; achromophorous group; a self-doped electronic conductive polymer; ahydrolyzable alkoxysilane; a polymer chain carrying grafts including acarbonyl group, a sulfonyl group, a thionyl group or a phosphonyl group;a group capable of trapping free radicals such as a crowded phenol or aquinone; a dissociating dipole such as an amide, a sulfonamide or anitrile; a redox pair such as a disulfide, a thioaamide, a ferrocene, apheno-thiazine, a bis(dialkylaminoaryl) group, a nitroxide or anaromatic jiide; a complexing ligand; a zwitterion, an optically orbiologically active amino acid or a polypeptide; a chiral group.

[0041] The choice of substituent Z enables to adjust the properties of acompound of the invention.

[0042] A particular family of compounds of the invention is the one inwhich Z represents a group R_(D)Y—. The compounds in which Y is —SO₂—are especially preferred.

[0043] In an embodiment, R_(D) is selected from alkyl, alkenyl,oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl orthia-alkenyl radicals having from 1 to 24 carbon atoms, or from aryl,arylalkyl, alkylaryl or alkenylaryl radicals having from 5 to 24 carbonatoms.

[0044] In another embodiment, R_(D) is selected from alkyl or alkenylradicals having from 1 to 12 carbon atoms and possibly comprising atleast one heteroatom O, N or S in the main chain or in a lateral chain,and/or possibly carrying a hydroxy group, a carbonyl group, an aminogroup or a carboxyl group.

[0045] A substituent R_(D) may be a polymer radical, for example anoligo(oxyalkylene) radical. The compound of the invention then appearsin the form of a polymer carrying an ionic group —[Y—N—SO_(x)—R_(F)]⁻,M⁺.

[0046] R_(D) may be a recurring unit of a polymer, for example anoxyalkylene unit or a styrene unit. The compound of the invention thenappears in the form of an polymer in which at least part of therecurring units carry a lateral group on which an ionic group−[Y—N—SO_(x)—R_(F)]⁻, M⁺ is bonded. By way of example, apoly(oxyalkylene) in which at least certain oxyalkylene units carry asubstituent −[Y—N—SO_(x)—R_(F)]⁻, M⁺, or a polystyrene in which at leastcertain styrene units carry a substituent −[Y—N—SO_(x)—R_(F)]⁻, M⁺, forexample [styrenyl-Y—N—S(O)_(x)—R_(F)]⁻, may be mentioned.

[0047] A particular category of compounds of the invention comprises thecompounds in which the substituent R_(D) has at least one anionicionophoric group and/or at least one cationic ionophoric group. Theanionic group may for example be a carboxylate (—CO₂—), a sulfonatefunction (—SO₃—), a sulfonimide function (—SO₂NSO₂—) or a sulfonamidefunction (—SO₂N—). The cationic ionophoric group may for example be aniodonium, sulfonium, oxonium, ammonium, amidinium, guanidinium,pyridinium, uimdazolium, uimdazolinium, triazolium, phosphonium orcarbonium group. The cationic ionophoric group may totally or partiallyplay the role of the cation M.

[0048] When R_(D) includes at least ethylenic unsaturation and/or acondensable group and/or a group which is dissociable by thermal orphotochemical means or by ionic dissociation, the compounds of theinvention are reactive compounds which may be subject topolymerizations, cross-linkings or condensations, optionally with othermonomers. They may also be used to fix ionophoric groups on the polymerscarrying a suitable reactive function.

[0049] A substituent R_(D) may be a mesomorphous group or achromophorous group or a self-doped electronically conductive polymer ora hydrolyzable alkoxysilane.

[0050] A substituent R_(D) may include a group capable of trapping freeradicals, for example, a hindered phenol or a quinone.

[0051] A substituent R_(D) may also include a bipolar dissociatingagent, for example, an amide function, a sulfonamide function or anitrile function.

[0052] A substituent R_(D) may also include a redox couple, for example,a disulfide group, a thioamide group, a ferrocene group, a phenothiazinegroup, a bis(dialkylaminoaryl) group, a nitroxide group or an aromaticimide group.

[0053] A substituent R_(D) may also include a complexing ligand or anoptically active group.

[0054] Another category of compounds of the invention comprisescompounds in which R_(D)—Y— represent an amino acid, or an optically orbiologically active polypeptide.

[0055] According to a variant, a compound of the invention comprises asubstituent R_(D) which represents a radical having a valency v higherthan 2, itself including at least one group R_(F)—S(O)_(x)—N—Y—. In thiscase, the negative charges present on the anionic part of the compoundof the invention should be compensated by an appropriate number ofcations or ionophorous cationic groups M.

[0056] When a compound of the present invention corresponds to theformula R_(F)—S(O)_(x)—N—Z, in which Z is an electroattractive groupwhich is not bonded to the nitrogen which carries the negative charge bya group Y, Z is advantageously selected from the group consisting of—CN, —OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and —SC₂F₄H, —O—CF═CF₂,—SCF═CF₂, n being a whole number from 1 to 8. Z may also be a radicalC_(n)F_(2n+1)CH₂—, n being a whole number from 1 to 8, or among theheterocyclic compounds, in particular those derived from pyridine,pyrazine, pyrimidine, oxadiazole, thiadiazole, which are fluorinated ornon-fluorinated. Z may also represent a recurring unit of a polymer. Thecompound of the invention is then in the form of a polymer in which atleast part of the recurring units carry a lateral group on which anionic group —[(N—SO_(x)—R_(F))—, M⁺] is fixed. By way of example, apolymer comprising one of the following recurring units may bementioned:

[0057] or a polyzwitterion of a conductive polymer which is a self-dopedpolyaniline in which the recurring unit is:

[0058] The compounds of the invention may be obtained, by a process inwhich a compound R_(F)SO_(x)—L is reacted with a compound [A—N—Z]^(n−)mnM^(m+), R_(F), x, M and Z being as previously defined, L representingan electronegative starting group such as a halogen, a N-imidazoylradical, a N-triazoyl radical, a radical R_(F)SO_(x+1)— and A representsa cation M^(m+), a trialkylsilyl group, a trialkylgermanyl group, atrialkylstannyl group or a tertiaryalkyl group, in which the alkylsubstituents have from 1 to 6 carbon atoms. By way of example, thereaction of a fluorosulfonyl fluoride with a bi-salt of cyanamideaccording to the following reaction scheme may be mentioned:

FSO₂—F+[NaNCN]⁻ Na⁺

NaF+[FSO₂—NCN]⁻ Na⁺.

[0059] The reaction of a substituted aniline withtrifluoromethanesulfonic anhydride may also be mentioned.

[0060] The compounds in which Z represents R_(D)Y— may be obtained by aprocess in which a compound R_(D)—Y—L is reacted with a compound[R_(F)SO_(X)—N—A]^(n−)m nM^(m+). By way of example of such a process,the reaction of a perfluorosulfonamide or one of its salts with asulfonyl halide may be mentioned.

[0061] The use of a compound [A—N—Z]^(n−)nM^(m+) in which A is atertiary alkyl group is advantageous, because such a group is a protonprecursor by formation of the corresponding alkene. The use of atrialkylsilyl is especially interesting when the starting group is afluorine atom, by reason of the very high stability of the bond F—Si.

[0062] When there is used a compound [A—N—Z]^(n−)nM^(m+) in which A isthe proton, it is advantageous to carry out the reaction in the presenceof a tertiary base or crowded base T capable of forming the salt L⁻(HT⁺)by combination of the proton, in order to promote the formation of thecompound of the invention. The base may be selected from alkylamines(for example triethylamine, diisopropylamine, quinuclidine),1,4-diazobicyclo[2,2,2]octane (DABCO); pyridines (for example pyridine,alkylpyridines, dialkylaminopyridines); imidazoles (for exampleN-alkylimidazoles, imidazo[1,1-a]pyridine); amidines (for example1,5-diazabicyclo[4,3,0]non-5-ene (DBN),1,8-diazabicyclo[5,4,0]undec-7-ene (DBU)); guanidines (for exampletetramethyl guanidine,1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (HPP).

[0063] By way of example of such a process, the process in which asulfonyl chloride R_(D)SO₂Cl is reacted with a perfluorosulfonamide inthe presence of DABCO may be mentioned.

[0064] A compound according to the invention may also be obtained byreacting perfluorosulfonic acid or one of its salts with a compound(R^(i))₃P═N⁻Z in which the R^(i) represent independently from oneanother an alkyl radical, an aryl radical or a dialkylamino radical. Inthe same manner, an acid R_(D)SO_(x)—OH or one of its salts may bereacted with a compound (R^(i))₃P═N—SO_(x)R_(F). By way of example, thereaction of a sodium alkylsulfonate with R_(F)SO₂N═P(C₆H₅)₃ may bementioned.

[0065] The cation of a compound obtained according to either one of theprocesses described above may be replaced by known processes of cationexchange, either by precipitations or selective extractions, or by theuse of ion exchange resins.

[0066] In addition, the substituent R_(D) of a compound of the inventionmay be modified by means of known reactions. For example, a substituentR_(D) which comprises an allyl group may be converted by reaction with aperoxide to give an epoxidized substituent R_(D). A group —NHR may beconverted into a vinylester group by reaction with a strong base such aspotassium tert-butoxide, then with vinylchloroformate. The processesenabling to carry out these modifications and others are available tothose skilled in the art. Of course, the functions carried by radicalR_(A) and R which could interfere with the reactions leading to thepreparation of the compounds of the invention may be temporarilyprotected by means of known techniques. For example, an amine functionmay be protected by a group t-BOC (tertiobutoxycarbonyl) which is stablein the presence of bases T but which is easily removed by treatment inan acid medium.

[0067] The ionic compounds of the present invention comprise at leastone ionophoric group on which substituents which can vary to a largeextent are fixed. Taking into account the large choice possible for thesubstituents, the compounds of the invention enable the production ofproperties of ionic conduction in most of the organic media, liquids orpolymers having even a low polarity. The applications are important inthe field of electrochemistry, in particular for storing energy inprimary or secondary generators, in supercapacitances, in combustiblebatteries and in electroluminescent diodes. The compatibility of theionic compounds of the invention with polymers or organic liquids enableto induce noted anti-static properties, even when the content of ioniccompound is extremely low. The compounds of the invention which arepolymers, as well as polymer compounds obtained from the compounds ofthe invention having the property of polymerizing or co-polymerizing,show the properties mentioned above with the advantage of having animmovable anionic charge. This is why another object of the presentinvention resides in an ionically conductive material consisting of anionic compound of the present invention in solution in a solvent.

[0068] In an embodiment, the ionic compound used for the preparation ofan ionically conductive material is selected from the compounds in whichthe cation is ammonium, or a cation derived from a metal, in particularlithium or potassium, zinc, calcium, metals of rare earths, or anorganic cation, such as a substituted ammonium, an imidazolium, atriazolium, a pyridinium, a 4-dimethylamino-pyridinium, said cationsoptionally carrying a substituent on the carbon atoms of the cycle. Theionically conductive material thus obtained has an elevated conductivityand solubility in solvents, resulting from weak interactions between thepositive charge and the negative charge. Its field of electrochemicalstability is extended, and it is stable in reducing as well as oxidizingmedia. Moreover, the compounds which have an organic cation and amelting point lower than 150° C., in particular imidazolium, triazolium,pyridinium, 4-dimethylainino-pyridiniun compounds have an intrinsicelevated conductivity, even in the absence of solvent, when they are inmolten phase.

[0069] The materials with ionic conduction which incorporate a compoundof the invention in which R_(F) is a fluorine atom or a perhalogenatedalkyl radical having from 1 to 12 carbon atoms, or a perhalogenatedalkylaryl radical having from 6 to 9 carbon atoms are interesting to theextent that the low interactions between the atoms of fluorine of thechain result in high solubility and conductivity, even in the case wherethe remainder of the molecule contains groups having a tendency to givestrong interactions such as conjugated aromatic radicals or zwitterions.

[0070] The choice of a compound of the invention in which R_(F) isselected from the radicals R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— orCF₃C(R_(A))F— enable it to very precisely adapt the properties of theionically conductive material by selecting the substituent R_(A) in anappropriate manner. In particular, they permit to rely, with a reducednumber of fluorine atoms, on the properties of dissociation and ofsolubility inherent to the anionic charges of the perfluorinatedsystems. These groups are easily accessible from industrial productssuch as tetrafluoroethylene or tetrafluoropropylene. The reducedquantity of fluorine renders these compounds less susceptible toreduction by metals which are even electropositive, such as aluminum,magnesium or especially lithium.

[0071] The properties of the ionically conductive material may also beadapted by the choice of the substituent R_(D).

[0072] The choice for R_(A) or R_(D) of an alkyl group, an aryl group,an alkylaryl group or an arylalkyl group, enables to introduce into theionically conductive material properties of mesogene type, in particularalkyl groups having from 6 to 20 carbon atoms, aryl-alkyl groups, inparticular those containing the biphenyl entity which form phases of theliquid crystal type. Properties of conduction in phases of the liquidcrystal, nematic, cholesteric or discotic types, are interesting forapplications relating to optical posting or to reduce the mobility ofanions in the electrolytes, in particular in polymer electrolytes,without affecting the mobility of the cations. This characteristic isimportant for applications in electrochemical generators, andparticularly those involving lithium cations.

[0073] When the substituent R_(A) is a mesomorphous group or a groupcomprising at least one ethylenic unsaturation and/or a condensablegroup and/or a group which is dissociable by thermal means, byphotochemical means or by ionic dissociation, or when R_(D) is asubstituent containing one of these groups, the ionically conductivematerial easily forms polymers or copolymers which are polyelectrolytes,either intrinsically when the polymer carries solvating groups, or byaddition of a polar solvent of a liquid or polymer type, or by mixturewith such a solvent. These products have a conductivity which is solelydue to the cations, which constitutes a property which is very useful inthe applications of the electrochemical generator type. In low molarfraction in a copolymer, they produce antistatic properties which arestable and are little dependent on humidity, and promote the fixation ofcationic coloring materials, this property being useful for textilefibres and lasers with coloring materials.

[0074] The presence of a substituent R_(A) or R_(D) which is aself-doped electronically conductive polymer improves the stability ofthe ionically conductive material as compared to outside agents. Theconductivity is stable in time, even at elevated temperatures. Incontact with metals, these materials give very low interface resistanceand, in particular, protect ferrous metals or aluminum againstcorrosion.

[0075] When the substituent R_(A) or R_(D) is an hydrolyzablealkoxysilane, the ionically conductive material may form stable polymersby the simple mechanism of hydrolysis-condensation in the presence ofwater, thereby enabling treatment of oxide, silica, silicate, inparticular glass surfaces to induce properties of surface conduction,antistatic properties, or to promote the adhesion of polar polymers.

[0076] When the substituent R_(A) or R_(D) is a group comprising a freeradical trap such as a congested phenol or a quinone, the ionicallyconductive material has the following advantages and properties: it actsas an antioxidant with no volatility and being compatible with polarmonomers and polymers, to which it additionally provides antistaticproperties.

[0077] When the substituent R_(A) or R_(D) comprises a dissociatingdipole such as an amide, a sulfonamide or a nitrile, the ionicallyconductive material has an improved conductivity in media with low oraverage polarity, in particular in solvating polymers, which enables tominimize, even to remove the addition of solvents or volatileplasticizing agents.

[0078] The presence of a substituent R_(A) or R_(D) which contains aredox couple such as a disulfide, a thioamide, a ferrocene, apheno-thiazine, a bis(diallylaminoaryl) group, a nitroxide, an aromaticimide, enables introduction into the ionically conductive materialshuttle redox properties which are useful as an element for theprotection and the equalization of the charge of electrochemicalgenerators, in photoelectrochemical systems, in particular forconverting light into electricity, in systems for modulating light ofthe electrochrome type.

[0079] The presence of a substituent R_(A) or R_(D) which is acomplexing ligand in an ionically conductive material enables chelationof metallic cations, in particular those which possess an elevatedcharge (2, 3 and 4), in the form of a complex which is soluble inorganic media, including aprotic media, and enable transportation ofthese cations in particular in the form of an anionic complex, insolvating polymers. The metallic cations of elevated charge are indeedimmovable in solvating polymers. This type of complexing gives redoxcouples which are particularly stable, with certain cations oftransition metals (Fe, Co . . . ) or certain rare earths (Ce, Eu . . .).

[0080] The ionically conductive materials containing a compound of theinvention in which R_(D) is an alkyl or an alkenyl substituent whichcontains at least one heteroatom selected from O, N and S have acomplexing and plasticizing property, in particular in polar polymersand especially polyethers. The heteroatoms N and S are selectivelycomplexing for cations of transition metals, Zn and Pb.

[0081] When a substituent R_(D) alkyl or alkenyl additionally carries anhydroxy group, a carbonyl group, an amino group, a carboxyl group, anisocyanate group or a thioisocyanate group, the ionic compound of theinvention may give by polycondensation a polymer or copolymer and theionically conductive material which contains such a polymer or copolymershows polyelectrolyte properties.

[0082] The presence, in the ionically conductive material of theinvention, of a compound in which R_(D) is selected from radicals aryl,arylalkyl, alkylaryl or alkenylaryl, in which the lateral chains and/orthe aromatic nuclei comprise heteroatoms such as nitrogen, oxygen,sulfur, improves dissociation and increases the possibility of formingcomplexes depending on the position of the heteroatom (pyridine), or ofgiving by duplicating oxidation conjugated polymers or copolymers(pyrrol, thiophene).

[0083] When the ionically conductive material contains a compound of theinvention in which R_(D) represents a recurring unit of a polymer chain,the material constitutes a polyelectrolyte.

[0084] A compound of the invention in which the substituent Z isselected from the group consisting of —OC_(n)F_(2n+1), —OC₂F₄H,—SC_(n)F_(2n+1) and —SC₂F₄H, —OCF═CF₂, —SCF═CF₂, n being a whole numberfrom 1 to 8, is a precursor of stable monomers and polymers inparticular towards oxygen even at temperatures higher than 80° C. whendealing with polymers. An ionically conductive material which containssuch a compound is therefore particularly suitable as as electrolyte ofa combustible battery.

[0085] An ionically conductive material of the present inventioncomprises an ionic compound of the invention in solution in a solvent.

[0086] The solvent may be an aprotic liquid solvent, a polar polymer ora mixture thereof.

[0087] The aprotic liquid solvent is selected for example among linearethers and cyclic ethers, esters, nitriles, ritro derivatives, amides,sulfones, sulfolanes, alkylsulfamides and partially halogenatedhydrocarbons. Particularly preferred solvents include diethylether,dimethoxyethane, glyme, tetrahydrofurane, dioxane,dimethyltetrahydrofurane, methylformate or ethylformate, propylene orethylene carbonate, alkyl carbonates (such as dimethyl carbonate,diethyl carbonate and methylpropyl carbonate), butyrolactones,acetonitrile, benzonitrile, nitromethane, nitrobenzene,dimethylformamide, diethylformamide, N-methylpyrrolidone,dimethylsulfone, tetramethylene sulfone and tetraalkylsulfonamideshaving from 5 to 10 carbon atoms.

[0088] The polar polymer may also be selected from a cross-linked or noncross-linked solvating polymer, with or without grafted ionic groups. Asolvating polymer is a polymer which includes solvating units containingat least one heteroatom selected from sulfur, oxygen, nitrogen andfluorine. By way of example of solvating polymers, there may bementioned polymers with linear structure, comb or block type, which mayor may not form a network, based on poly(ethylene oxide), or copolymerscontaining an ethylene oxide, propylene oxide or allylglycidyletherunit, polyphorphazenes, cross-linked network based on polyethyleneglycol cross-linked with isocyanates, or networks obtained bypolycondensation and carrying groups which permit the incorporation ofcross-linkable groups. Block copolymers in which certain blocks carryfunctions which have redox properties may also be mentioned. Of course,the above list is not limiting, and all the polymers having solvatingproperties may also be used.

[0089] An ionically conductive material of the present invention maysimultaneously comprise an aprotic liquid solvent selected from theabove-mentioned aprotic liquid solvents and a polar polymer solventcomprising units containing at least one heteroatom selected fromsulfur, nitrogen, oxygen and fluorine. It may comprise 2 to 98% liquidsolvent. By way of example of such a polar polymer, polymers whichmainly contain units derived from acrylonitrile, vinylidene fluoride,N-vinylpyrolidone or methyl methacrylate may be mentioned. Theproportion of aprotic liquid in the solvent may vary from 2%(corresponding to a plasticized solvent) to 98% (corresponding to agelled solvent).

[0090] An ionically conductive material of the present invention mayadditionally contain a salt commonly used in the prior art for preparingan ionically conductive material. Among the salts which may be used inadmixture with an ionic compound according to the invention, a saltselected from the perfluoroalcanesulfonates,bis(perfluoroalylsulfonyl)imides, bis(perfluoro-alkylsulfonyl)methanesand tris(perfluoroalkylsulfonyl)methanes is particularly preferred.

[0091] Of course, an ionically conductive material of the invention mayadditionally contain the additives known to be used with this type ofmaterial, for example mineral or organic charges in the form of a powderor fibres.

[0092] An ionically conductive material of the invention may be used asan electrolyte in an electrochemical generator. It is therefore anobject of the present invention to provide an electrochemical generatorcomprising a negative electrode and a positive electrode, both beingseparated by an electrolyte, wherein the electrolyte is an ionicallyconductive material as defined above. According to a particularembodiment, such a generator comprises a negative electrode consistingof metallic lithium, or one of its alloys, optionally in the form ofnanometric dispersion in lithium oxide, or a double nitride of lithiumand a transition metal, or an oxide with low potential having thegeneral formula Li_(1+y+x/3)Ti_(2−x/3)O₄ (0≦x≦1, 0≦y≦1), or carbon andcarbonated products resulting from pyrolysis of organic materials.According to another embodiment, the generator comprises a positiveelectrode selected from vanadium oxide VO_(x) (2≦x≦2,5), LiV₃O₈,Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x≦1; 0≦y≦1), magnesium spinelsLi_(y)Mn_(1−x)M_(x)O₂ (M═Cr, Al, V, Ni, 0≦x≦0,5 ; 0≦y≦2), organicpolydisulfides, FeS, FeS₂, ferric sulfate Fe₂(SO₄)₃, phosphates andphosphosilicates of iron and of lithium of olivine structure, orproducts wherein iron is substituted by manganese, used alone or inadmixtures. The collector of the positive electrode is preferablyaluminum.

[0093] An ionically conductive material of the present invention mayalso be used in a supercapacitance. Another object of the presentinvention is consequently a supercapacitance utilizing at least onecarbon electrode with high specific surface, or an electrode containinga redox polymer, in which the electrolyte is an ionically conductivematerial as defined above.

[0094] An ionically conductive material of the present invention mayalso be used for the p or n doping of a polymer with electronicconduction and this use constitutes another object of the presentinvention.

[0095] In addition, an ionically conductive material of the presentinvention may be used as an electrolyte in an electrochrome device. Anelectrochrome device in which the electrolyte is an ionically conductivematerial according to the invention is another object of the presentinvention.

[0096] It has been noted that the strong dissociation of the ionicspecies of the compounds of the invention result in a stabilization ofthe carbocations, in particular those in which there is a conjugationwith oxygen or nitrogen and, surprisingly in a strong activity of theproponic form of the compounds of the invention on certain monomers. Itis also an object of the invention to provide for the utilization of theionic compounds as photoinitiators which constitute sources of Bronstedacids, catalysts for the polymerization or cross-linking of monomers orprepolymers capable of cationic reaction, or as a catalysts for themodification of polymers.

[0097] The process of polymerization or cross-linking of monomers orprepolymers capable of cationic reaction is characterized in that thereis used a compound of the invention as photoinitiator constituting asource of acid which catalyzes the polymerization reaction. Thecompounds according to the invention in which the cation is a grouphaving a bond —N═N+, —N═N—, a sulfonium group, an iodonium group, or anoptionally substituted arene-ferrocenium cation, possibly incorporatedin a polymeric skeleton, are particularly preferred.

[0098] The choice of substituent R_(F) on the one hand, and ofsubstituents R_(D) or Z on the other hand, is made in a manner toincrease the solubility of said compound in the solvents used for thereaction of the monomers or prepolymers, and as a function of thedesired properties for the final polymer. For example, the choice of anon-substituted alkyl radicals gives solubility in low polar media. Thechoice of radicals comprising a group oxa or a sulfone gives solubilityin polar media. The radicals including a sulfoxide group, a sulfonegroup, and a phosphine oxide group, a phosphonate group, respectivelyobtained by the addition of oxygen on the atoms of sulfar or phosphorus,may provide improved properties with respect to adhesion, glossiness,resistance to oxidation or UV to the polymer obtained. The monomers andpolymers which may be polymerized or cross-linked by means of thephotoinitiators of the present invention are those which may be subjectto a cationic polymerization.

[0099] Among the monomers, those which include a cyclic ether function,a cyclic thioether function or a cyclic amino function, vinyl compounds(more particularly vinyl ethers), oxazolines, lactones and lactames maybe mentioned.

[0100] Among the monomers of the cyclic ether or thioether type,ethylene oxide, propylene oxide, oxetane, epichlorhydrin,tetrahydrofurane, styrene oxide, cyclohexene oxide, vinylcyclohexeneoxide, glycidol, butylene oxide, octylene oxide, glycidyl ethers andesters (for example glycidyl methacrylate or acrylate, phenyl glycidylether, bisphenol A diglycidylether or its fluorinated derivatives),cyclic acetals having from 4 to 15 carbon atoms (for example dioxolane,1,3-dioxane, 1,3-dioxepane) and spiro-bicyclo dioxolanes may bementioned.

[0101] Among the vinyl compounds, vinyl ethers constitute a veryimportant family of monomers which are subject to cationicpolymerization. By way of example, there may be mentioned ethyl vinylether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether,ethyleneglycol monovinyl ether, diethyleneglycol divinyl ether,butanediol monovinyl ether, butanediol divinyl ether, hexanediol divinylether, ethyleneglycol butyl vinyl ether, triethyleneglycol methyl vinylether, cyclohexanedimenthanol monovinyl ether, cyclohexanedimethanoldivinyl ether, 2-ethylhexyl vinyl ether, poly-THF-divinyl ether having aweight between 150 and 5000, diethyleneglycol monovinyl ether,trimethylolpropane trivinyl ether, aminopropyl vinyl ether, and2-diethylaminoethyl vinyl ether.

[0102] Other vinyl compounds may include by way of example1,1-dialkylethylenes (for example isobutene), aromatic vinyl monomers(for example styrene, x-alkylstyrene, such as x-methylstyrene,4-vinylanisole, acenaphthene), N-vinyl compounds (for exampleN-vinylpyrolidone or N-vinyl sulfonamides).

[0103] Among the prepolymers, there may be mentioned the compounds inwhich the epoxy groups are carried by an aliphatic chain, an aromaticchain, or a heterocyclic chain, for example glycidyl ethers or bisphenolA which are ethoxylated by 3 to 15 ethylene oxide units, siloxaneshaving lateral groups of the type epoxycyclohexene-ethyl obtained byhydrosilylation of copolymers of dialkyl, alkylaryl or diaryl siloxanewith methyl hydrogenosiloxane in the presence of vinylcyclohexene oxide,condensation products of the type sol-gel obtained from triethoxy ortrimethoxy silapropylcyclohexene oxide, urethanes incorporating reactionproducts of monovinylether butanediol and an alcohol of a functionhigher than or equal to 2,With an aliphatic or aromatic di or triisocyanate.

[0104] The process of polymerization according to the invention consistsin mixing at least one monomer or prepolymer capable of cationicpolymerization and at least one ionic compound of the invention, andsubjecting the mixture obtained to actinic or D radiation. Preferably,the reaction mixture is subjected to irradiation after having beenshaped as a thin layer having a thickness lower than 5 mm, preferably inthe form of a thin film having a thickness lower than or equal to 500μm. The duration of the reaction depends on the thickness of the sampleand the power of the source at the active wavelength k. It is defined bythe speed in front of the source, which is comprised between 300 nm/minand 1 cm/min. Layers of final material having a thickness higher than 5mm may be obtained by repeating many times the operation consisting ofspreading a layer and treating it byu irradiation.

[0105] Generally, the quantity of photoinitiator used is between 0.01and 15% by weight with respect to the weight of the monomer orprepolymer, preferably between 0.1 and 5% by weight.

[0106] An ionic compound of the present invention may be used asphotoinitiator in the absence of solvent, for example when it isintended to polymerize liquid monomers in which the ionic compound usedas photoinitiator is soluble or easily dispersible. This type of use isparticularly interesting, since it permits to get rid of problemsassociated with solvents (toxicity, flammability).

[0107] An ionic compound of the present invention may also be used asphotoinitiator in the form of a homogenous solution in a solvent whichis insert during polymerization, which solution is ready to use andeasily dispersible, in particular in the case where the mixture to bepolymerized or cross-linked has a high viscosity.

[0108] As an example of inert solvent, there may be mentioned volatilesolvents, such as acetone, methyl-ethyl ketone and acetonitrile. Thesesolvents will merely be used for diluting the products to be polymerizedor cross-linked (to make them less viscous, especially when dealing witha prepolymer). They will be eliminated by drying after polymerization orcross-linking. Non-volatile solvents may also be mentioned. Anon-volatile solvent is also used for diluting the products that areintended to be polymerized or cross-linked, and to dissolve the saltA⁺X⁻ of the invention used as photoinitiator, however, it will remain inthe material formed and will thus act as a plasticizing agent. By way ofexample, propylene carbonate, γ-butyrolactone, ether-esters of mono-,di-, tri- ethylene or propylene glycols, ether alcohol of mono-, di-,tri- ethylene or propylene glycols, plasticizing agents such as phthalicacid esters or citric acid esters may be mentioned.

[0109] According to another embodiment of the invention, there is usedas solvent or diluent a compound which is reactive towardspolymerization, which has a low molecular weight and low viscosity andwhich will act simultaneously as a polymerizable monomer and as solventor diluent for more viscous monomers or prepolymers used jointly. Afterthe reaction, these monomers which have been used as solvents will bepart of the macromolecular network finally obtained, their integrationbeing greater when dealing with bi-functional monomers. The materialobtained after irradiation is now free of products having a lowmolecular weight and an appreciable vapour tension, or susceptible tocontaminate objects with which the polymer is in contact. By way ofexample, a reactive solvent may be selected from mono- and di- vinylethers of mono-, di-, tri-, tetra- ethylene and propylene glycols,N-methylpyrolidone, 2-propenylether of propylene carbonate which iscommercially available for example under the designation PEPC from ISP,New Jersey, United States.

[0110] To irradiate the reaction mixture, the irradiation may beselected from ultraviolet radiation, visible radiation, X-rays, γ raysand β radiation. When ultraviolet light is used as an actinic radiation,it may be advantageous to add to the photoinitiators of the inventionphotosensitizers intended to permit an efficient photolysis withwavelengths less energetic than those corresponding to a maximum ofabsorption of the photoinitiator, such as those emitted by industrialdevices (λ≈300 nm with mercury vapour lamps in particular). Suchadditives are known, and by way of non-limiting example, there may bementioned anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine,tetracene, xanthone, thioxanthone, acetophenone, benzophenone,1,3,5-triaryl-2-pyrazolines and derivatives thereof, in particularderivatives which are substituted on the aromatic nuclei by alkyl, oxa-or aza- alkyl radicals enabling among others to change the absorptionwavelength. Isopropylthioxantone is a preferred example ofphotosensitizer when an iodonium salt according to the invention is usedas a photoinitiator.

[0111] Among the various types of radiation mentioned, ultravioletradiation is particularly preferred. On the one hand, it is easier touse than the other radiations mentioned above. On the other hand,photoinitiators are in general directly sensitive to UV rays andphotosensitizers especially since the difference of energy (δγ) islower.

[0112] The ionic compounds of the invention may also be used inassociation with initiators of radical types which are producedthermally or by the action of actinic radiation. It is thus possible topolymerize or cross-link mixtures of monomers or prepolymers containingfunctions in which the modes of polymerization are different, forexample monomers or prepolymers which polymerize by free radicalreaction and monomers or prepolymers which polymerize by cationicpolymerization. This possibility is particularly advantageous forproviding interpenetrated networks having different physical propertiesfrom those which would be obtained by a mere mixture of polymersoriginating from corresponding monomers. The vinyl ethers are not or arevery little active by radical initiation. It is therefore possible, in areaction mixture containing a photoinitiator according to the invention,a free radical initiator, at least one monomer of vinyl ether type andat least one monomer comprising non-activated double bonds such as thoseof the allyl groups, to carry out a separate polymerization of each typeof monomer. On the other hand, it is known that monomers which aredeficient in electrons, such as esters or amides of fumaric acid, maleicacid, acrylic or methacrylic acid, itaconic acid, acrylonitrile,methacrylonitrile, maleinides and derivatives thereof, are formed in thepresence of electron enriched vinyl ethers, charge transfer complexeswhich give alternating polymers 1:1 by free radical initiation. Aninitial excess of vinyl monomers with respect to this stoichiometryenables preservation of polymerizable functions by pure cationicinitiation. Triggering of the activity of a mixture of free radicalinitiator and cationic initiator according to the invention may becarried out simultaneously for the two reactants in the case for exampleof isolation with actinic radiation of a wavelength in which thephotoinitiators of the invention and the free radical initiatorsselected are active, for example λ=250 nm. By way of example ofinitiators, the following commercial products may be mentioned: Irgacure184®, Irgacure 651®, Irgacure 261®, Quantacure DMB®, Quantacure ITX®.

[0113] It may also be advantageous to use the two types ofpolymerization in a sequential manner to form first prepolymers whichare easy to produce and in which hardening, adhesiveness, solubility aswell as cross-linking degree may be is modified by initiating theactivity of the cationic initiator. For example, a mixture of athermo-dissociable free radical initiator and a cationic photoinitiatoraccording to the invention enables to provide sequential polymerizationand cross-linkings, first under the action of heat, then under theaction of actinic radiation. In a similar manner, if a free radicalinitiator and a cationic photoinitiator according to the invention areselected, the first being photosensitive to longer wavelengths than theones which initiate the photoinitiator according to the invention, thereis obtained a cross-linking in two controllable steps. Free radicalinitiators may for example be Irgacure 651®, enabling initiation freeradical polymerizations at wavelengths of 365 nm.

[0114] It is also an object of the invention to use ionic compounds ofthe invention for reactions of chemical amplification of photoresistsfor microlithography. During such a use, a film of a material comprisinga polymer and an ionic compound of the invention is subject toirradiation. The irradiation causes the formation of the acid byreplacement of the cation M with a proton, which catalyzes thedecomposition or transformation of the polymer. After decomposition ortransformation of the polymer on the parts of the film which have beenirradiated, the formed monomers or the polymer which has been convertedare eliminated and what remains is an image of the non-exposed parts.For this particular application, it is advantageous to use a compound ofthe invention which is in the form of a polymer consisting essentiallyof styrenyl recurring units having an ionic substituentR_(F)—SO_(x)—N⁻—. These compounds enable to produce, after photolysis,products which are non-volatile, and therefore non-odorous when dealingwith sulfides. Among the polymers which may thus be modified in thepresence of a compound of the invention, there may be mentioned forexample polymers containing ester groups or terdoalkyl arylether groups,for example poly(phthaldehydes), polymers of bisphenol A and a diacid,polytertiobutoxycarbonyl oxy-styrene, polytertiobutoxy-α-methyl styrene,polyditertiobutylfiimarate-co-allyltrmethylsilane and polyacrylates of atertiary alcohol, in particular tertiobutyl polyacrylate. Other polymersare described in J. V. Crivello et al, Chemistry of Materials 8,376-381, (1996).

[0115] The ionic compounds of the present invention, which have a highthermal stability, have numerous advantages with respect to the knownsalts of the prior art. They have initiation and propagation speedswhich are comparable or higher than those obtained by means ofcoordination anions of the type PF₆—, AsF₆— and especially SbF₆—. Inaddition, the coefficient of diffusion of the anion R_(F)—SO_(x)—N— ishigher than the one of hexafluorometallate anions or tetrafluoroborateanions or phenylborate anions. These properties are explained by thedelocalization of the negative charge and the flexibility of the anionaround the bond S—N.

[0116] In the compounds of the present invention, the pairs of ions havea very high dissociation, which enables the expression of the intrinsiccatalyst properties of the cation M^(m+), in which the active orbits areeasily exposed to the substrates of the reaction, especially in variousmedia. Most of the important reactions of organic chemistry may thus becarried out under easy conditions, with excellent yields, and facilitatethe separation of the catalyst from the reaction mixture. The appearanceof asymmetric induction by the use of an ionic compound according to theinvention which carries a chiral group is particularly important becauseof its generality and its ease of application. It should be noted thatthe chiral perfluorinated molecules [R_(F)SO₂—N—SO₂R_(F)]⁻, 1/mM^(m+)are unknown and would only present a negligible optical activity becauseof the low polarizable character of the perfluorinated groups.Consequently, it is another object of the present invention to usecompounds of the invention as catalysts in Friedel and Craft reactions,Diels and Alder reactions, aldolization reactions, additions of Michael,allylation reactions, reactions of pinacolic coupling, reactions ofglycosilation, reactions of openings of oxetane cycles, reactions ofmethathesis of alcenes, polymerization of the Ziegler-Natta type,polymerizations of the type methathesis by opening of the cycle andpolymerizations of the type methathesis of acyclic dienes. The preferredionic compounds of the invention for use as catalyst in the reactionsmentioned above are those in which the cation is selected from lithium,magnesium, copper, zinc, tin, trivalent metals, including rare earths,platinoids, their organometallic couples, in particular metallocenes.

[0117] The compounds of the invention may also be used as a solvent forcarrying out chemical, photochemical, electrochemical,photoelectrochemical reactions. For this particular use, ionic compoundsin which the cation is an imidazolium, a triazolium, a pydridinium or a4-dimethylamino-pyridinium are preferred, said cation optionallycarrying a substituent on the carbon atoms of the cycle. The compoundsbeing used in liquid form, those which have a melting point lower than150° C., more particularly lower than 100° C. are particularlypreferred.

[0118] The inventors have also found that the anionic charge carried bythe group R_(F)—SO_(x)—N⁻Z exerts a stabilizing effect on electronicconductors of the conjugated polymer type, and that the use of acompound in which the substituent Z comprises a long alkyl chain wouldcause these polymers to be soluble in the usual organic solvents, evenin doped state. Grafting of these charges on the polymer itself givespolymers in which the global charge is cationic, which are soluble inorganic solvents and provide, in addition to their stability, propertiesof anti-corrosiveness towards metals, such as aluminum and ferrousmetals. It is also an object of the present invention to provideelectronically-conductive materials comprising an ionic compound of thepresent invention in which the cationic part is a polycation consistingof a “p” doped conjugated polymer. The preferred ionic compounds forthis application are those in which the substituent Z contains at leastone alkyl chain having from 6 to 20 carbon atoms. By way of example, thecompounds in which Z is R_(D)Y—, R_(D) being an alkyl radical, may bementioned. There may also be mentioned compounds in which R_(F) isR_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— in whichR_(A)— represents an alkyl radical. Additionally, compounds in which Zrepresents an aromatic nucleus carrying an alkyl radical may also bementioned.

[0119] Coloring materials of cationic type (cyanines) are used more andmore frequently as sensitizers of photographic films, for the opticalstoring of information (optical disks which are accessible in writing),for lasers. The tendency of these conjugated molecules to be stackedover one another when they are in solid phases limits their use, becauseof the variations of the optical properties with respect to the isolatedmolecule. The use of ionic compounds of the invention for themanufacture of cationic coloring materials in which the counter ions,eventually fixed to this same molecule, correspond to the functions ofthe invention, enables to reduce the phenomenons of aggregation,including in solid polymer matrices, and to stabilize these coloringmaterials. It is another object of the invention to provide acomposition of colouring material, characterized in that it contains anionic compound according to the invention. The particularly preferredionic compounds of this application are those in which the negativecharge(s) of the ionic group R_(F)—SO_(x)—N⁻—Z are either fixed to themolecule of the colouring material, or they constitute the counter-ionof the positive charges of the colouring material. By way of example ofsuch compounds, the following compounds may be mentioned:

[0120] The present invention is illustrated by the following examples,however, it is not limited thereto.

[0121] Examples 1 to 7 describe the preparation of some compounds usedas reactants for the synthesis of the ionic compounds of the presentinvention. Examples 8 to 78 illustrate the preparation of compoundsaccording to the invention and their uses.

EXAMPLE 1 Trifluoromethanesulfonamide

[0122] To a suspension under strong stirring of 140.53 g (1.8 moles) ofammonium carbamate H₂NCO₂NH₄ (commercially available from Aldrich) in 11of dichloromethane at 0° C., there is added drop-wise during 2 hours282.13 g (1 mole) of trifluoromethanesulfonic anhydride (CF₃SO₂)20(commercially available from Aldrich) diluted in 250 ml ofdichloromethane. Carbon dioxide evolved according to the followingreaction:

(CF₃SO₂)₂O+1,5H₂NCO₂NH₄→CF₃SO₃ ⁻NH₄ ⁺+CF₃SO₂NH⁻NH₄ ⁺+1,5 CO₂

[0123] After 3 hours at 0° C., the reaction is continued for 24 hours atroom temperature, and dichloromethane was evaporated and the product wasreclaimed with 400 ml of water. The addition of 250 ml of a solution ofhydrochloric acid 4 M has permitted release oftrifluoromethanesulfonamide CF₃SO₂NH₂ which was extracted with threefractions of 200 ml of ether. After drying the ether phase (600 ml) withmagnesium sulfate, the product was recovered after evaporation of etherand purified by sublimation under secondary vacuum at 60° C. There isobtained 137.16 g of trifluoromethanesulfonamide CF₃SO₂NH₂ (92% yield)having a purifity characterized by a proton and fluorine RMN higher than99%.

[0124] The corresponding sodium salt was prepared by reactingtrifluoromethanesulfonamide with sodium carbonate Na₂CO₃ in water (20%in excess). After evaporation of water and drying, the product obtainedwas reclaimed in acetonitrile and the excess of carbonate was removed byfiltration. After evaporation of acetonitrile and drying, there isobtained a quantative amount of sodium salt oftrifluoromethanesulfonamide CF₃SO₂NHNa.

[0125] Microanalysis has given: H 0.52 (0.59); C 7.22 (7.02); N 8.41(8.19); F 33.82 (33.32); Na 13.21 (13.44); S 18.65 (18.74).

[0126] The lithium salt CF₃SO₂NHLi and potassium salt CF₃SO₂NHK havebeen obtained by a similar process, by replacing sodium carbonaterespectively with lithium carbonate and potassium carbonate.

EXAMPLE 2 Fluorosulfonamide

[0127] The compound was prepared under similar conditions to thosedescribed in Example 1, by replacing the trifluoromethanesulfonamideCF₃SO₂NH₂ by 182.11 g (1 mole) of fluorosulfonic anhydride (FSO₂)2O(commercially available from SST Corporation) previously purified byvacuum distillation. There is obtained 80.25 g of fluorosulfonamideFSO₂NH₂ (81% yield), having a purity characterized by a proton andfluorine RMN higher than 99%. The corresponding sodium salt was preparedby dosing an aqueous solution at 0° C. of fluorosulfonamide FSO₂NH₂ witha titrated solution of sodium hydroxide until reaching theneutralization point determined by pH-metry. After lyophiliration anddrying under vacuum during 24 hours, the sodium salt offluorosulfonamide FSO₂NHNa was recovered quantitatively.

[0128] Microanalysis has given: H 0.78 (0.83); N 11.32 (11.57); F 15.12(15.69); Na 18.66 (18.99); S 26.01 (26.48).

[0129] The salts of lithium FSO₂NHLi and of potassium FSO₂NHK have beenobtained by a similar process, by replacing sodium hydroxiderespectively by lithium hydroxide and potassium hydroxide.

EXAMPLE 3 Pentafluoroethanesulfonyl Chloride

[0130] In 600 ml of ether cooled to −78° C. under argon, 60 g (244mmoles) of pentafluoroethyl iodine C₂F₅I (commercially available fromStrem Chemicals) were condensed. Under stirring, there is then added 153ml of a solution 1.6 M of methyllithium in ether (244 mmoles),(commercially available from Fluka). After 5 minutes, there wasintroduced ≈20 g (≈312 mmoles) of sulfur dioxide SO₂ into the solution,the reaction was continued during 2 hours at −78° C. Then, the solutionwas allowed to reach room temperature during 2 hours, and after 1 hourat room temperature, the solvents were evaporated. After drying, 44.51 gof lithium pentafluoroethanesulfinate C₂F₅SO₂Li (96% yield) wererecovered.

[0131] A flow of chlorine Cl₂ was then allowed to pass in 200 ml ofwater containing 28.5 g (150 mmoles) of lithiumpentafluoroethanesulfinate C₂F₅SO₂Li. Rapidly, there appeared a secondphase, denser than water which was extracted with fractions of 25 ml ofanhydrous dichloromethane. After drying the organic phase with magnesiumsulfate, 26.55 g of pentafluoroethanesulfonyl chloride C₂F₅SO₂Cl (81%yield) were recovered by fractionate distillation. The product has apurity characterized by a fluorine RMN fluorine higher than 99%.

EXAMPLE 4 Perfluorobutanesulfonamide

[0132] To 30.21 g (100 mmoles) of perfluoro-1-butanesulfonyl fluorideC₄F₉SO₂F (commercially available from Aldrich) and 8.91 g (100 mmoles)of ethyl carbarnate C₂H₅O₂CNH₂ in 100 ml of anhydrous tetrahydrofaraneat 0° C., there is added in portions 1.75 g (220 mmoles) of 95% lithiumhydride LiH at 95% (commercially available from Aldrich). After stirringfor 72 hours under argon, the reaction mixture was centrifuged andfiltered to remove the precipitate of lithium fluoride LiF and theexcess of lithium hydride. The solvent was thereafter evaporated and theproduct obtained wasreclaimed in 100 ml of water. After adding 3.5 g(200 mmoles) of lithium hydroxide monohydrate, the reaction mixture washeated to a reflux overnight to hydrolyze the ester function. Aftercooling, the reaction mixture was given a pH≈1 by addition of a solutionof hydrochloric acid 10 M in order to remove the carboxyl function whichis present, and it was extracted with three fractions of 50 ml of etherafter 24 hours of stirring. After drying of the organic phase withmagnesium sulfate and evaporation, 27.2 g ofperfluoro-1-butanesulfonamide C₄F₉SO₂NH₂ (91% yield) having a puritycharacterized by a proton and fluorine RMN higher than 99%, wererecovered after drying under vacuum.

[0133] The corresponding sodium salt was prepared by reactingperfluoro-1-butanesulfonamide with sodium carbonate Na₂CO₃ in water (20%in excess). After evaporating water and drying, the product obtained wasreclaimed in tetrahydrofurane and the excess of carbonate was removed byfiltration. After evaporation of tetrahydrofurane and drying, the sodiumsalt of perfluoro-1-butanesulfonamide C₄F₉SO₂NHNa was obtainedquantitatively.

[0134] Microanalysis has given: H 0.25 (0.31); C 15.35 (14.96); N 4.63(4.36); F 54.1 (53.25); Na 7.36 (7.16); S 10.35 (9.98).

[0135] The lithium and potassium salts were obtained by a similarprocess, by replacing lithium carbonate respectively with sodiumcarbonate and potassium carbonate.

EXAMPLE 5 Pentafluoroethanesulfonamide

[0136] 10.93 g of pentafluoroethanesulfonyl chloride C₂F₅SO₂Cl, preparedas in Example 3, were added slowly to 50 ml of a 1 M solution of sodiumbis(trimethylsilyl)amide ((CH₃)₃Si)₂NNa in tetrahydrofurane (50 mmoles,commercially available from Aldrich) at −20° C.

[0137] After 2 hours at −20° C., the solvent was evaporated and theproduct was reclaimed in 50 ml of water, the pH was brought to ≈2 andthe aqueous phase was extracted with two fractions of 20 ml of ether.After drying the organic phase with magnesium sulfate, the recoveredproduct was sublimated under vacuum. After 24 hours, 6.17 g ofpentafluoroethanesulfonamide C₂F₅SO₂NH₂ (62% yield) having a puritycharacterized by a proton and fluorine RMN higher than 99% wererecovered on a cold finger.

[0138] The corresponding sodium salt was prepared by reactingperfluoroethanesulfonamide with sodium carbonate Na₂CO₃ in water (20% inexcess). After evaporating water and drying, the product obtained wasreclaimed in tetrahydrofurane and the excess of carbonate was removed byfiltration. After evaporating tetrahydrofurane and drying, the sodiumsalt of perfluoroethanesulfonamide C₂F₅SO₂NHNa was obtainedquantitatively.

[0139] Microanalysis has given: H 0.42 (0.46); C 10.35 (10.87); N 6.73is (6.34); F 42.01 (42.97); Na 10.89 (10.4); S 14.25 (14.5).

[0140] Salts of lithium and potassium were obtained by a similarprocess, by replacing sodium carbonate respectively with lithium andpotassium carbonate.

EXAMPLE 6 Potassium Triflinate

[0141] To a suspension in 50 ml of anyhydrous acetonitrile at −18° C. of22.64 g (100 mmoles) of the bi-potassium salt of2,2-dimercapto-1,3,4-thiadiazole (commercially available from Aldrich),there is added 17.36 g (103 mmoles) of trifluoromethanesulfonyl chlorideCF₃SO₂Cl. After 48 hours while stirring at room temperature, thereaction mixture was filtered to remove potassium chloride and thepoly(2,2-dimercapto-1,3,4-thia-diazole) formed during the reactionaccording to the following reaction scheme:

[0142] After evaporating the solvent and drying under vacuum at roomtemperature during 24 hours, 16.3 g of potassium triflinate CF₃SO₂K (95%yield) were recovered with a purity characterized by a fluorine RMNhigher than 98%.

[0143] Microanalysis has given: C 6.72 (6.98); F 32.6 (33.11); S 18.32(18.62); K 22.29 (22.71).

EXAMPLE 7 3-Sulfonyl-1,2,4-Triazine Chloride

[0144] 28.83 (300 mmoles) of 3-amino-1,2,4,-triazine (commerciallyavailable from Aldrich) were added to a mixture under stirring of 100 mlof concentrated hydrochloric acid and 30 ml of glacial acetic acid. Thereaction mixture was brought to −10° C. and 22.42 g (325 mmoles) ofsodium nitrite NaNO₂ in 35 ml of water were added slowly. Thediazotation reaction was allowed to proceed for 1 hour. At the sametime, a flow of sulfur dioxide SO₂ was passed through a frit in 300 mlglacial acetic acid until saturation. Following this, 7.5 g of copperchloride (I) CuCl were added and the addition of sulfur dioxide wascontinued until the colour of the reaction mixture went fromyellow-green to blue-green. After having brought the temperature of thereaction mixture to lower than 10° C., the previously prepared diazoniumwas added during 30 min. A small amount of ether was added to decreasethe quantity of foam which is formed after each addition. After the endof diazonium addition, the reaction mixture was poured into 1 liter of amixture of water and ice (1:1). After melting of the ice, a yellow oilwas separated in a decanting flask, and the aqueous phase was extractedwith two fractions of 100 ml ether. After adding the ether phase to theoil which has been collected, the solution was washed with aconcentrated solution of sodium bicarbonate until reaching neutrality,and then with water, and finally it was dried with magnesium sulfate.After evaporation of the solvent, 35.1 g of 3-sulfonyl-1,2,4-triazine(65% yield) having a purity characterized by proton and fluorine RMNhigher than 98% were collected after vacuum distillation.

[0145] Microanalysis has given: C 20.6 (20,1); H 0.6 (1.1); N 23.6(23.4); S 17.6 (17.9); Cl 19.3 (19.7).

EXAMPLE 8 3-Chloropropanesulfonyl(Trifluoromethanesulfonyl)-Imide

[0146] 17.7 g (100 mmoles) of 3-chloropropanesulfonyl chlorideCl(CH₂)₃SO₂Cl and 37.44 g (200 mmoles) of potassiumtrifluoromethanesulfonamide CF₃SO₂NHK were reacted at 0° C. in 50 ml oftetrahydrofurane anhydride. After 3 hours at 0° C., and 24 hours at roomtemperature, tetrahydrofurane was evaporated and the product wascrystallized in 40 ml of water, recovered by filtration and dried. Therewere obtained 23.6 g of the potassium salt oftrifluoromethanesulfonyl(3-chloropropanesulfonyl)-imideCl(CH₂)₃SO₂NKSO₂CF₃ (72% yield) having a purity characterized by protonand fluorine RMN higher than 99%.

[0147] Microanalysis has given: H 1.76 (1.85); C 14.23 (14.66); N 4.56(4.27); F 17.78 (17.39); S 19.09 (19.56); Cl 10.28 (10.82); K 11.45(11.93).

[0148] By a similar process, the potassium salt offluorosulfonyl(3-chloropropane-sulfonyl)imide (65% yield) was obtainedfrom the potassium salt of fluorosulfonamide obtained in Example 2 andthe potassium salt ofpentafluroethane-sulfonyl(3-chloropropanesulfonyl)imide (82% yield) wasobtained from the potassium salt of pentafluorosulfonamide obtained inExample 5.

[0149] Lithium salts were obtained in quantitative yields by treatmentof the potassium salts in anhydrous tetrahydrofurane with astoichiometric quantity of anhydrous lithium chloride, filtration of thereaction medium, evaporation of the solvent and drying under vacuum.

[0150] These three salts are soluble in most of the usual organicsolvents (tetrahydrofurane, acetonitrile, dimethylformamide, ethylacetate, glymes, . . . ) and in aprotic solvating polymers such as poly(ethylene oxide). In this latter solvent at a concentration O/K of 14/1,they have an ionic conductivity greater than 10⁻³ S.cm⁻¹ at atemperature of 100° C.

[0151] These salts may be easily grafted on different substratesincluding a site which is sufficiently nucleophilic such as analcoholate, an amide or a methylide.

EXAMPLE 9 2,2,2-Trifluoroethanesulfonyl(Trifluoromethanesulfonyl)Imide

[0152] To a solution in 30 ml of anhydrous acetonitrile at 0° C. of 9.13g (50 mmoles) of 2,2,2-trifluoroethanesulfonyl CF₃CH₂SO₂Cl (commerciallyavailable from Aldrich) and 7.45 g (50 mmoles) oftrifluoromethanesulfonamide CF₃SO₂NH₂, 7.91 g (100 mmoles) of anhydrouspyridine were added drop-wise. After 2 hours at 0° C., the reaction wascontinued during 48 hours at room temperature. The reaction mixture wasthen filtered to remove the pyridinium hydrochloride formed. Thereaction mixture was then stirred during 48 hours with 5.79 g (50mmoles) of lithium phosphate Li₃PO₄. After filtration, evaporation ofthe solvent and drying, 14.6 g of the lithium salt oftrifluoromethanesulfonyl(2,2,2-trifluoroethane-sulfonyl) imideCF₃CH₂SO₂NLiSO₂CF₃ (97% yield) were obtained.

[0153] Microanalysis has given: H 0.72 (0.67); Li 2.48 (2.3); C 11.56(11.97); N 4.88 (4.65); F 38.02 (37.86); S 21.56 (21.3).

[0154] This salt has a conductivity of 2.3×10⁻⁴ S.cm⁻¹ at 60° C. in poly(ethylene oxide) at a concentration of O/Li of 12/1.

[0155] It has a proton presenting an acid character enabling to givereactions of nucleophilic substitution in the presence of a base with,for example, alkyl or acid halides.

EXAMPLE 10 N-Methyl-Sulfonyl(Trifluoromethanesulfonyl)Imide

[0156] Under argon, there is added drop-wise during 2 hours 100 ml of a2M solution of methylamine CH₃NH₂ (200 mmoles), (commercially availablefrom Aldrich) in tetrahydrofurane to a solution, at −20° C. under strongstirring, of 13.5 g (100 mmoles) of sulfuyl chloride SO₂C₁₂ in 50 ml ofanhydrous dichloromethane. After 3 hours at −20° C., the reactionmixture was subjected to centrifugation to remove the precipitate ofmethylammonium hydrochloride CH₃NH₃ ⁺Cl⁻ formed. After evaporation oftetrahydrofurane, the remaining liquid was distilled under vacuum. Thereare obtained 12.82 g of N-methyl-chlorosulfonamide ClSO₂NH(CH₃) (95%yield) having a purity characterized by a proton RMN higher than 98%.

[0157] 6.48 g (50 mmoles) of N-methyl-chlorosulfonamide were thenreacted in 30 ml of anhydrous tetrahydrofurane with 7.45 g (50 mmoles)of trifluoromethanesulfonamide, and with 11.22 g (100 mmoles) of1,4-diazabicyclo[2.2.2]octane (DABCO). After 48 hours, the reactionmixture was filtered to remove the DABCO hydrochloride precipitateformed. After evaporation of the solvent, the product obtained wasreclaimed in 20 ml of ethanol and 40.91 g (100 mmoles) of potassiumacetate were added. The precipitate was then formed. Afterrecrystallization, filtration and drying, 9.95 g of potassiumtrifluoromethanesulfonyl(N-methylsulfonyl)imide CF₃SO₂NKSO₂NH(CH₃) (71%yield) were recovered, in which the purity characterized by proton andfluorine RMN is higher than 98%.

[0158] Microanalysis has given: H 1.31 (1.44); C 8.38 (8.57); N 9.85(9.99); F 20.89 (20.34); S 22.35 (22.88); K 13.52 (13.95).

[0159] By a similar process, the potassium salt oftrifluoromethanesulfonyl(N-ethyl-sulfonyl)imide was obtained fromethylamine and the potassium salt oftrifluoromethanesulfonyl(N-propyl-sulfonyl)imide was obtained frompropylamine.

[0160] The lithium salts were prepared quantitatively by ionic exchangebetween the potassium salts and lithium chloride in anhydroustetrahydrofurane.

[0161] These compounds have a labile proton permitting to give reactionsof nucleophilic substitution in the presence of a base with alkyl andacid halides for example.

EXAMPLE 11 5-Formyl-2-Furanesulfonyl(Trifluoromethanesulfonyl)Imide

[0162] To 9.91 g (50 mmoles) of the sodium salt of5-formyl-2-furanesulfonic acid (commercially available from Aldrich) in30 ml of anhydrous dimethylformamide at 0° C., 6.35 g (50 mmoles) ofoxalyl chloride ClCOCOCl in solution in 20 ml of anhydrousdichloromethane were added slowly, then, after 2 hours at 0° C., 18.72 g(100 mmoles) of the potassium salt of trifluoromethanesulfonamideCF₃SO₂NHK were added. This reaction was continued for 48 hours at roomtemperature, and the solvent was evaporated and the product obtained wascrystallized in 40 ml of water. After filtration and drying, 10.88 g ofthe potassium salt oftrifluoromethanesulfonyl(5-formyl-2-furane-sulfonyl)imide (63% yield)having a purity determined by fluorine and proton RMN higher than 99%were recovered.

[0163] Microanalysis has given: H 1.01 (0.88); C 20.55 (20.87); N 4.15(4.06); F 16.91(16.51); S 18.17 (18.57); K 11.76 (11.32).

[0164] By the same process, the potassium salt offluorosulfonyl(5-formyl-2-furane-sulfonyl)imide was obtained.

[0165] The aldehyde function enables grafting of this salt on substratescontaining a group capable of reacting with this function, for example,an amino group or a double bond.

EXAMPLE 12 Allylsulfonyl(Trifluoromethanesulfonyl)Imide

[0166] To 14.41 g (100 mmoles) of the sodium salt of 2-propene-sulfonicCH₂═CHCH₂SO₃Na in suspension in 60 ml of anhydrous acetonitrile at −20°C., 11.9 g (100 mmoles) of thionyl chloride SOCl₂ diluted in 20 ml ofbenzene were added drop-wise during 2 hours. The mixture was allowed tostand overnight at −20° C., and it was centrifuged to remove sodiumchloride formed and the solvents were evaporated by means of a rotaryevaporator provided with a membrane pump. The liquid obtained was thendistilled under vacuum in a short column to give 10.97 g of2-propene-sulfonyl CH₂═CHCH₂SO₂Cl (78% yield) characterized by a protonRMN. 7.03 g (50 mmoles) of this compound were then reacted with 18.72 g(100 mmoles) of potassium trifluoro-methanesulfonamide CF₃SO₂NHK in 60ml of an anhydrous acetonitrile at 0° C. during 2 hours, followed by areaction period at room temperature for 24 hours. After evaporation ofthe solvent, the product was recrystallized in 20 ml of water. Afterfiltration and drying, 17.22 g of the potassium salt oftrifuoromethane-sulfonyl(2-propenesulfonyl)imide CH₂═CHCH₂SO₂NKSO₂CF₃(66% yield) having a purity characterized by a proton and fluorine RMNhigher than 98%.

[0167] Microanalysis has given: H 1.68 (1.73); C 16.22 (16.49); N 4.6(4.81); F 19.12 (19.57); S 22.29 (22.01); K 13.23 (13.42).

[0168] According to the same process, the potassium salt ofpentafluoroethanesulfonyl(2-propene-sulfonyl)imide (69% yield) wasobtained from the potassium salt of pentafluoroethanesulfonamideobtained in Example 5.

[0169] These salts have the characteristic of homo- or copolymerizing bya polymerization which is initiated by free radical polymerization or bymeans of an olefin polymerization catalyst of the Ziegler-Natta type,such as a zircanocene, and more generally, they are characterized bybeing able to undergo chemical reactions inherent to ethylenic bonds.

EXAMPLE 13 3,4-Epoxypropane-1-Sulfonyl(Trifluoromethanesulfonyl)Imide

[0170] To 11.65 g (40 mmoles) of the potassium salt oftrifluoromethanesulfonyl(2-propenesulfonyl)imide, obtained in Example12, in 100 ml of water, there were added 6.9 g (40 mmoles) of3-chloroperoxybenzoic acid obtained according to the procedure describedby Schwartz & Blumbergs (J. Org. Chem., (1964), 1976). After 1 hour ofstrong stirring, the solvent was evaporated and the residue wasrecrystallized in 15 ml ethanol. After filtration and drying, 7.5 g ofthe potassium salt of2,3-epoxy-propane-1-sulfonyl(trifluoromethane-sulfonyl)imide (61% yield)having a purity characterized by proton and fluorine RMN higher than 98%were recovered.

[0171] Microanalysis has given: H 1.84 (1.64); C 15.2 (15.63); N 4.99(4.56); F 18.01 (18.55); S 20.15 (20.87); K 12.01 (12.72).

[0172] According to the same procedure, there is obtained the potassiumsalt of a 2,3-epoxypropane-1-sulfonyl(pentafluoroethanesulfonyl)imidefrom the potassium salt ofpentafluoroethanesulfonyl(2-propene-sulfonyl)imide obtained in Example12.

[0173] Lithium salts were obtained by treating potassium salts inanhydrous tetrahydrofurane with the stoichiometric quantity of anhydrouslithium chloride, filtration of the reaction mixture, evaporation of thesolvent and drying under vacuum.

[0174] These salts may be homo- or copolymerized by means of apolymerization initiated by anionic or cationic means. More generally,they may undergo chemical reactions which are inherent to oxetanes.

[0175] The homopolymer of2,3-epoxypropane-1-sulfonyl(trifluoromethane-sulfonyl)imide was preparedby polymerization in tetrahydroflurane which was initiated by anionicpolymerization with potassium tert-butoxide, then the polysalt oflithium was prepared by ionic exchange with anhydrous lithium chloride.The latter has a conductivity in a gelled medium (21% by weight ofpolyacrylonitrile, 38% ethylene carbonate, 33% propylene carbonate, 8%homopolymer) of 1.1×10⁻³ S.cm⁻¹ at 30° C. The cationic transport numberof this electrolyte is 0.82. Moreover, this homopolymer is soluble inmost of the usual organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in aproticsolvating polymers.

EXAMPLE 14 Vinylsulfonyl(Trifluoromethanesulfonyl)Imide

[0176] To a solution at 0° C. and under argon of 8.15 g (50 mmoles) of2-chloro-1-ethane-sulfonyl chloride ClCH₂CH₂SO₂Cl (commerciallyavailable from Aldrich) and 7.45 g (50 mmoles) oftrifluoromethanesulfonamide CF₃SO₂NH₂ in 25 ml of anhydroustetrahydrofurane, there is added drop-wise during 30 min, a solution of16.83 g (150 mmoles) of DABCO diluted in 25 ml of anhydroustetrahydrofurane. After the end of the addition of the base, thereaction is continued during 2 hours at 0° C., and then for 24 hours atroom temperature. The reaction mixture was then filtered to remove theDABCO hydrochloride formed. Then, 2.12 g of anhydrous lithium chloride(50 mmoles) were added, the reaction mixture was stirred during 24hours, and it is again filtered to remove the DABCO hydrochlorideformed. After evaporation of tetrahydrofurane and drying, 11.89 g of thelithium salt of trifluoromethanesulfonyl(vinylsulfonyl)imideCH₂═CHSO₂NLiSO₂CF₃ (98% yield) were recovered having a purity which ischaracterized by a proton and fluorine RMN higher than 98%.

[0177] Microanalysis has given: H 1.28 (1.23); Li 2.78 (2.83); C 14.91(14.7); N 5.82 (5.71); F 22.5 (23.25); S 25.8 (26.16).

[0178] According to the same process, the lithium salt ofperfluorobutanesulfonyl)vinyl-sulfonyl)imide (99% yield) was obtainedfrom the perfluorobutanesulfonamide obtained in Example 4.

[0179] These salts may be homo- or copolymerized by a polymerizationwhich is initiated by free radical polymerization. More generally, theymay undergo chemical reactions which are inherent to activated vinylbonds, in particular additions of Michael, with for example analcoholate.

EXAMPLE 15 7,8-Octene-3,6-Oxa-1-Sulfonyl(Trifluoromethane-Sulfonyl)Imide

[0180] To 2.2 g (25 mmoles) of ethylene glycol vinyl etherCH₂═CHO(CH₂)2OH in 60 ml of anhydrous dimethylformamide, there is added6.13 g (25 mmoles) of the lithium salt ofvinylsulfonyl-(trifluoromethanesulfonyl)imide, obtained in Example 14,5.87 g of anhydrous potassium carbonate K₂CO₃ (42.5 mmoles) and 330 mg(1.25 mmoles) of a crown ether, 18-Crown-6 (acting as complexing agentof the potassium cation). The reaction mixture was then stirred underargon at 85° C. After 48 hours, the reaction mixture was filtered on afritted glass of porosity N° 3, and the solvent was evaporated underreduced pressure. After drying, the compound was recrystallized in 10 mlof water containing 1.86 g (25 mmoles) of anhydrous potassium chlorideKCl. After filtration and drying, 5.66 g of the potassium salt of7,8-octene-3,6-oxa-1-sulfonyl(trifluoromethane-sulfonyl)imide (62%yield) having a purity characterized by a proton and fluorine RMN higherthan 98% was recovered.

[0181] Microanalysis has given: H 3.12 (3.03); C 23.26 (23.01); N 3.77(3.83); F 15.89 (15.6); S 17.12 (17.55); K 10.23 (10.7).

[0182] There is obtained a quantitative yield of the lithium salt bytreatment of the potassium salt in anhydrous tetrahydrofurane with thestoichiometric quantity of anhydrous lithium chloride, filtration of thereaction mixture, evaporation of the solvent and drying under vacuum.

[0183] This salt may be homopolymerized by cationic polymerization. Itmay also be copolymerized by cationic polymerization, optionally bypolymerization which is alternated with an unsaturated monomer. Moregenerally, it may undergo chemical reactions which are characteristic ofalkyl vinyl ethers.

[0184] The homopolymer prepared by polymerization in anhydrousacetonitrile initiated by cationic polymerization withbis(trifluoromethanesulfonyl)imide has a conductivity at a concentrationof 0.8 M in a mixture of dimethylcarbonate and ethylene carbonate (2:1)of 6×10⁻³ S.cm⁻¹ at 30° C. Moreover, this homopolymer is soluble in mostof the known organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in the aproticsolvating polymers such as poly (ethylene oxide).

[0185] EXAMPLE 16

4-Styrenesulfonyl(Trifluoromethanesulfonyl)Imide

[0186] In 100 ml of anhydrous tetrahydrofurane under argon at 0° C.,20.27 g (10 mmoles) of 4-styrenesulfonyl chloride CH₂═CHC₆H₄SO₂Cl(commercially available from Monomer-Polymer & Dajac Laboratories) werereacted with 14.91 g (10 mmoles) of trifluoromethane-sulfonamideCF₃SO₂NH₂ and 22.44 g (20 mmoles) of (DABCO). After 2 hours at 0° C. and48 hours at room temperature, the solution was filtered to remove theDABCO hydrochloride formed, and it was thereafter treated with 424 mg(10 mmoles) of anhydrous lithium chloride, which is stored and weighedin a glove box. Immediately, a precipitate of DABCO hydrochloride wasformed and the reaction mixture was then again filtered after stirringfor 6 hours. After evaporation and drying under vacuum, during 24 hoursat room temperature, 31.16 g of the lithium salt oftrifluoromethane-sulfonyl(4-styrenesulfonyl)imide were recovered whichhave a purity characterized by a proton and fluorine RMN higher than97%.

[0187] Microanalysis has given: H 2.4 (2.2); Li 2.56 (2.16); C 33.15(33.65); N 4.79 (4.36); F 17.14 (17.74); S 19.51 (19.96).

[0188] According to the same process, lithium salts offluorosulfonyl(4-styrenesulfonyl)-imide (98% yield) were prepared fromthe fluorosulfonamide obtained in Example 2, ofpentafluoroethanesulfonyl(4-styrenesulfonyl)imide (97% yield) from thepentafluoroethanesulfonamide obtained in Example 5 and ofperfluorobutanesulfonyl(4-styrenesulfonyl)imide (99% yield) from theperfluorobutanesulfonamide obtained in Example 4.

[0189] These salts may be homo- or copolymerized by polymerizationinitiated by anionic, cationic and more particularly free radical means.They may also be grafted on a polymer matrix such as vinylidenepolyfluoride by irradiation.

[0190] The homopolymers obtained by free radical polymerization indeaerated water, initiated by cyanovaleric acid at 60° C. are soluble inthe usual organic solvents and in aprotic solvating polymers. Inpoly(ethylene oxide) at a concentration O/Li of 16/1, these salts have aconductivity ≈6×10⁻⁴ S.cm⁻¹ at 100° C. Moreover, in a concentratedsolution in acetone (≈1 M as lithium cation), these homopolymers may beused as catalysts in Diels-Alder reactions, and in this way they act aschemical micro-reactors.

Example 175-(4-Methylene-1,3-Dioxolane)-2-Furanesulfonyl(Trifluoromethanesulfonyl)Imide

[0191] 5.18 g (15 mmoles) of the potassium salt oftrifluoro-methanesulfonyl(5-formyl-2-furanesulfonyl)imide, 1.66 g (15mmoles) of 3-chloro-1,2-propanediol ClCH₂CH(OH)CH₂(OH) (commerciallyavailable from Aldrich) and ≈1 mg of p-toluenesulfonic acid monohydratewere mixed in 30 ml of toluene. An azeotropic distillation was thencarried out until the appearance of water in the Dean-Stark ceased to beobserved. After evaporation of the solvent, the product obtained wasrecrystallized in 10 ml of water. After filtration and drying, 5.13 g ofthe potassium salt of5-(4-methylene-1,3-dioxolane)-2-furanesulfonyl(trifluoromethane-sulfonyl)imide(82% yield) were recovered, and this product had a purity determined byproton and fluorine RMN higher than 98%.

[0192] Microanalysis has given: C 26.65 (26.93); H 1.89 (1.76); N 3.99(3.49); S 15.28 (15.98); F 13.8 (14.2); K 9.41 (9.74).

[0193] A quantitative yield of the lithium salts was obtained bytreatment of the potassium salt in anhydrous tetrahydrofurane with astoichiometric quantity of anhydrous lithium chloride, filtration of thereaction mixture, evaporation of the solvent and drying under vacuum.

[0194] This salt may be homo- or copolymerized by a polymerizationinitiated by cationic or free radical means. The homopolymer of thissalt was obtained by photopolymerization, which is initiated by cationicmeans through irradiation of tris(4-methylphenyl)sulfoniumhexafluoroantimonate with a U.V. lamp during 10 min at 36° C. It has aconductivity at a concentration of 0.5 M in tetraethylsulfamide(C₂H₅)₂NSO₂N(C₂H₅) of 4×10⁻³ S.cm⁻¹ at 20° C.

EXAMPLE 181-Acryloyl-2,2,2-Trifluoroethanesulfonyl-(Trifluoro-Methanesulfonyl)Imide

[0195] By operating in a glove box under argon, 7.53 g (25 mmoles) ofthe lithium salt oftrifluoromethanesulfonyl(2,2,2-tifluoro-ethanesulfonyl)imideCF₃CH₂SO₂NLiSO₂CF₃, prepared as in Example 9, were solubilized in 15 mlof anhydrous tetrahydrofurane. After adjusting the temperature of thissolution to −20° C., 50 ml of a 1 M solution (25 mmoles) intetrahydrofurane of sodium bis(trirethylsilyl)amide ((CH₃)₃Si)₂NNa(commercially available from Aldrich) were added. After 15 nin, there isslowly added 2.26 g (25 mmoles) of acryloyl chloride CH₂═CHCOClpreviously purified by distillation under vacuum. The reaction wascontinued during 2 hours at −20° C., and the reaction mixture wasfiltered to remove the precipitate of sodium chloride. The solvent wasthen evaporated and there is obtained after drying under vacuum at roomtemperature 8.7 g (98% yield) of the lithium salt oftrifluoromethanesulfonyl(1-acryloyl-2,2,2-trifluoroethanesulfonyl)imideCH₂═CHCOCH(CF₃)SO₂NLiSO₂CF₃ having a purity characterized by a protonand fluorine RMN higher than 98%.

[0196] Microanalysis has given: H 1.26 (1.14); Li 1.69 (1.95); C 20.06(20.29); N 3.79 (3.94); F 32.33 (32.1); S 18.26 (18.05).

[0197] This salt may be homo- or copolymerized by photopolymerization inthe presence of a photo-sensitizer.

[0198] There is prepared a mixture containing this salt (16 weight %), apoly(ethylene glycol) dimethacrylate having a molar weight of 600 g/mole(81 weight % commercially available from Aldrich), particles of silicahaving a specific surface of 300 m²/g (3 weight %, Aerosil, commerciallyavailable from Degussa AG) and xanthone. This solution was depositedwith a reel on a glass plate covered with a layer of tungsten trioxideWO₃ and a conductive sub-layer of tin oxide. There is obtained amembrane which is optically transparent in the visible range and whichadheres on the support by photopolymerization initiated by irradiationby means of U.V. lamp during 10 min at 32° C. Then, an electrochromesystem was prepared by assembling in a glove box a counter-electrodeconsisting of the deposit on a glass plate of a layer of hydrogenatediridium oxide H_(x)IrO₂ and a sub-layer of tin oxide. This electrochromehas given a variation of the optical absorption from 80% (discolouredstate) to 30% (coloured state) and good performances in cycling. is thuspossible to produce a number of cycles of coloring/discoloring greaterthan 20,000.

EXAMPLE 19 3-Maleimidopropanesulfonyl(Trifluoromethane Sulfonyl)Imide

[0199] To a solution of 2.43 g of maleimide (25 mmoles) in 20 ml ofanhydrous tetrahydrofurane there were added by portions 215 mg oflithium hydride LiH (27 mmoles). After 1 hour, a potassium salt oftrifluoromethanesulfonyl(3-chloropropane-sulfonyl)imide prepared as inExample 8 was added to the filtered solution. The reaction was continuedduring 24 hours at 60° C., and the reaction mixture was filtered toremove the potassium chloride KCl precipitate, the solvent wasevaporated and the product was dried. There is thus obtained 8.37 g (94%yield) of the lithium salt oftrifluoromethanesulfonyl(3-maleimido-propanesulfonyl)imide(—COCH═CHCO—)N(CH₂)₃SO₂NLiSO₂CF₃ having a purity characterized by aproton and fluorine RMN ≈96%.

[0200] Microanalysis has given: H 2.15 (2.26); Li 2.15 (1.95); C 26.72(26.97); N 7.66 (7.86); F 16.54 (16); S 18.25 (18).

[0201] According to the same process, the lithium salt ofpentafluoroethanesulfonyl(3-maleimido-propanesulfonyl)imide (98% yield)was obtained from the potassium salt ofpentafluoroethane-sulfonyl(3-chloropropanesulfonyl)imide obtained inExample 8.

[0202] These salts may be homopolymerized by free radical or anionicpolymerization or can be copolymerized by anionic or free radicalpolymerization optionally by polymerization alternated with an electrondonor monomer (N-vinyl-2-pyrrolidone, N-vinyl formamide, vinyl ether, .. . ).

[0203] The homopolymer prepared by polymerization in anhydroustetrahydrofurane at −78° C., initiated by anionic polymerization withsec-butyllithium, is soluble in the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide).

EXAMPLE 202-(Triethoxysilyl)Ethanesulfonyl(Trifluoromethane-Sulfonyl)Imide

[0204] In a Parr chemical reactor, there is introduced a solution of9.36 g (50 mmoles) of the potassium salt of trifluoromethanesulfonamideCF₃SO₂NHK and 264 mg of a potassium cation complexing crown ether,18-Crown-6, in 60 ml of anhydrous acetonitrile. After closing thereactor, flushing with argon was carried out during 15 min beforeisolating it. There were then introduced 6.41 g (50 mmoles) of sulfurdioxide SO₂ (commercially available from Fluka) and, after 10 min, 9.52g (50 mmoles) of vinyltriethoxysilane (commercially available fromFluka) in solution in 20 ml of anhydrous acetonitrile. After 6 hours atroom temperature, the temperature of the reactor was raised to 40° C.and was kept at that temperature during 48 hours, and the solvent wasevaporated. After drying under vacuum, the product was stored underargon. A quantitative yield of the potassium salt oftrifluoromethanesulfonyl(2-triethoxysilyl)ethane-sulfonyl)imide having apurity characterized by a fluorine and proton RMN higher than 99% wasrecovered.

[0205] Microanalysis has given: H 4.79 (4.34); K 8.27 (8.85); C 24.99(24.48); N 3.89 (3.17); F 12.15 (12.91); Si 6.75 (6.36); S 14.33(14.52).

[0206] The lithium salt was obtained by ionic exchange with lithiumchloride in tetrahydrofurane.

[0207] The corresponding acid was obtained by co-crushing in an agatemortar, under a glove box, the potassium salt with three equivalents(150 mmoles) of anhydrous ammonium hydrogen sulfate HSO₄NH₄(commercially available from Aldrich). Then, by secondary sublimationunder vacuum at 40° C.,trifluoromethanesulfonyl(2-(triethoxy-silyl)ethanesulfonyl)imide wasrecovered after 24 hours on a cold finger at a temperature of −40° C.

[0208] These salts enable formation of organosilicon networks by amechanism of hydrolysis-polycondensation. They also permits seeding ofglass base materials (fibre, glazing, . . . ) in order to modify theirsurface.

[0209] In addition, homopolymers or copolymers may be obtained withvarious alkoxysilanes in a protic medium, optionally in the presence ofa catalyst (acid, base, fluoride, . . . ).

[0210] A copolymer was prepared by polycondensation of the potassiumsalt of trifluoromethanesulfonyl-(2-triethoxysilyl)ethanesulfonyl)imidewith O-[20(trimethoxysilyl)ethyl]-O′-methylpolyethylene glycol ofmolecular weight 5,000 (commercially available from ShearwatersPolymers) (5:1 molar) in a water/methanol mixture by using as catalysttrifuoromethanesulfonyl(2-(triethoxysilyl)ethane-sulfonyl)imide. After afew hours, the solution was concentrated. Then, a pad of activatedcharcoal, previously de-gassed, having a specific surface of 1,500 m²/g(commercially available from Actitex), was impregnated with the viscousliquid obtained. After drying, this operation was repeated to improvethe impregnation. After having maintained the impregnated pad during 1week in a dryer at 50° C., two buttons having a diameter of 2 cm werecut out by stamping. A sheet of cigarette paper (commercially availablefrom Bolloré Technologies) was then impregnated with a viscous liquididentical to the one used to impregnate the carbon pad. This sheet wasplaced between the two buttons of impregnated carbon pad which were usedas carbon electrodes. After 1 week in a dryer at 50° C., and 2 daysunder vacuum at 60° C., there is obtained a “all-solid” electrochemicalsupercapacitance. This supercapacitance has given the followingperformances at 40° C.: a density of energy of 15 Wh/l (or a capacity of96 F/g of carbon for an electrode), a maximum power of 700 W/kg and goodresults in cycling (more than 10,000 cycles of charge/discharge between0 and 2V). Such a supercapacitance is particularly interesting in thefield of electronics because of the absence of volatile liquids.

[0211] A solution of the potassium salt oftrifluoromethanesulfonyl-(2-(triethoxysilyl)ethanesulfonyl)imide withO-[2-(triethoxysilyl)ethyl]-O′-methyl-polyethylene glycol having amolecular weight of 5,000 (commercially available from ShearwatersPolymers) (3:1 molar) was prepared in a mixture of water/methanol. Aglass plate pickled with nitric acid and dried at 100° C. was thereaftersoaked in the solution for a few minutes. After rincing with methanoland drying, a surface conductivity of 3×10⁻⁵ S (square) was measuredwhich is sufficient to give antistatic properties to the surface of theglass.

EXAMPLE 21Bis[3-(Trimethoxysilyl)Propyl]Aminosulfonyl(Trifluoro-Methanesulfonyl)Imide

[0212] 5.96 g (40 mmoles) of trifluoromethane-sulfonamide CF₃SO₂NH₂ and8.97 g (40 mmoles) of DABCO in 60 ml of anhydrous dichloromethane werecooled at −30° C. 5.4 g (40 mmoles) of sulfuryl chloride SO₂Cl₂ and12.54 g (40 mmoles) of bis[3-(trimethoxysilyl)propyl]amine of formula[(CH₃₀)₃Si(CH₂)₃]₂NH were then added drop-wise. The mixture was stirredduring 4 hours at −30° C., and for 24 hours at room temperature. 1.7 gof anhydrous lithium chloride LiCl were then added, the reaction mixturewas stirred during 24 hours, and filtered to removed the precipitate ofDABCO hydrochloride. After evaporation of the solvent and drying undervacuum, 21.88 g (98% yield) of the lithium salt ofbis[3-(trimethoxysilyl)propyl]aminosulfonyl(trifluoro-methanesulfonyl)having a purity characterized by a fluorine and proton RMN higher than98% were recovered.

[0213] Microanalysis has given: H 5.32 (5.41); Li 1.56 (1.24); C 27.66(27.95); N 5.22 (5.01); F 10.56 (10.2); Si 10.26 (10.06); S 11.67(11.48).

[0214] This compound has properties analogous to those of the compoundof Example 20 and may be used for the same applications.

[0215] This compound was polycondensed in a water/methanol mixture,utilizing a drop of concentrated hydrochloric acid as catalyst. After afew hours, the solvents were evaporated and the viscous liquid obtainedwas poured on a Teflon® plate. After one week in a dryer at 50° C., thematerial obtained was dried under vacuum at 100° C. during 48 hours, andcrushed under argon until obtaining a particle size of the order of 1micron. A composite electrolyte was then prepared by mixing this powderwith poly (ethylene oxide) of molecular weight M_(w)=3.10⁵ inacetonitrile. After having poured this dispersion in a glass ring andhaving evaporated the acetonitrile, there is obtained a film ofcomposite electrolyte having a good mechanical behaviour, a thickness of220 μm. This electrolyte has an ionic conductivity greater than 10-5S¹.cm⁻¹ at 60° C. The cationic transport number is 0.92.

EXAMPLE 22 N-Methyl-N-Vinylester-Sulfonyl(TrifluoromethaneSulfonyl)Imide

[0216] To 7.01 g (25 mmoles) of the potassium salt oftrifluoromethanesulfonyl(N-methylsulfonyl)imide CF₃SO₂NKSO₂NH(CH₃),prepared as in Example 10, in solution in 15 ml of anhydroustetrahydrofurane, there was slowly added under argon 25 ml of a 1 Msolution in tetrahydrofurane of potassium tert-butoxide (CH₃)₃COK (25mmoles, commercially available from Aldrich). After a few minutes, 2.66g (25 mmoles) of vinylchloroformate CH₂═CHO₂CCl (commercially availablefrom Lancaster), previously distilled under vacuum, were added. Thereaction is continued during 24 hours at room temperature. The reactionmixture was then filtered to remove the precipitate of potassiumchloride, the solvent was evaporated and the product was dried undervacuum. There is obtained 8.58 g (98% yield) of the potassium salt oftrifuoromethanesulfonyl-(N-methyl-N-vinylester-sulfonyl)imideCF₃SO₂NKSO₂N(CH₃)CO₂CH═CH₂.

[0217] Microanalysis has given: H 1.56 (1.73); C 17.56 (17.14); N 8.37(8); F 17.01 (16.27); S 18.56 (18.3); K 11.46 (11.16).

[0218] The lithium salt was obtained with quantitative yield by treatingthe potassium salt in anhydrous tetrahydrofurane with the stoichiometricquantity of anhydrous lithium chloride, filtration of the reactionmixture, evaporation of the solvent and drying under vacuum.

[0219] This salt may be homo- or copolymerized by means of apolymerization initiated by free radical.

[0220] There is produced a film of polymer electrolyte, having athickness of 30 μm, consisting of the lithium salt in solution in a poly(ethylene oxide) matrix having ethylenic unsaturations, at aconcentration O/Li=26/1, and containing 1% by weight of cyanovalericacid and 3% by weight of silica having a specific surface of 300 m²/g(Aerosil, commercially available from Degussa AG). This polymer wasobtained by polycondensation of polyethylene glycol of a molecularweight 1,000 with 3-chloro-2-chloromethyl-1-propene according to theprocedure described by Alloin & al. (J. Power Sources, (1995), 26,34-39). On the other hand, on a sheet of aluminum, a composite electrodehaving a thickness of 90 μm containing 45% by volume of vanadium dioxide(V₂O₅), 5% by volume of Ketjenblack® K600 (commercially available fromAkzo) as an additive of electronic conduction, and 50% by volume of apolymer electrolyte of the same composition as the one described above,was prepared. In a glove box under argon, the film of polymerelectrolyte was then deposited on the composite electrode, the filmbeing covered with a film of lithium with a thickness of 30 μm,deposited on a sheet of aluminum. The temperature of the assembly wasthen adjusted to 60° C. during 24 hours by applying a slight pressure.There is thus obtained an electrochemical generator with fixed anions,the lithium salt co-cross-linking with the double bonds of the polymermatrix. This generator gave a satisfactory result during cycling at 70°C. (72% of the capacity after 10 cycles at the 500th cycle ofcharge/discharge). Performances during calls for power were alsoimproved.

EXAMPLE 23 4-Perfluorovinyloxyphenylsulfonyl (Pentafluorosulfonyl)Imide

[0221] Under argon, at 9.95 g (50 mmoles) ofpentafluoroethanesulfonamide C₂F₅SO₂NH₂ in solution in 40 ml ofanhydrous tetrahydrofarane at −20° C., 10 ml of a 10 M solution ofbutyllithium in hexane C₄H₉Li (100 mmoles) were slowly added. After 2hours, 14.63 g of (3-(1,1,2,2-tetrafluoroethoxy)benzene sulfonylchloride (50 mmoles), prepared from(3-(1,1,2,2-tetrafluoroethoxy)aniline according to the general processdescribed in Example 7, were added. The reaction was continued during 24hours at −20° C., and 50 ml of a 10 M solution of butyllithium in hexaneC₄H₉Li (50 mmoles) were added. After 2 hours, the temperature wasallowed to rise to ambient and the solvents were evaporated. The productwas reclaimed in 30 ml of ethanol and recrystallized after addition of4.91 g (50 mmoles) of potassium acetate CH₃COOK. After filtration anddrying, 17.25 g of the potassium salt ofpentafluoroethanesulfonyl(3-(1,1,2-tri-fluorovinyloxy)benzenesulfonyl)imide(78% yield) having a purity characterized by a proton and fluorinehigher than 98% were obtained.

[0222] Microanalysis has given: H 1.1 (0.85); C 25.62 (25.37); N 2.69(2.96); F 33.1 (32.11); S 13.16 (13.55); K 8.95 (8.26).

[0223] According to the same process, the potassium salt oftrifluoromethane-sulfonyl(3-(1,1,2-trifluorovinyloxy)benzenesulfonyl)imide(98% yield) was obtained from trifluoromethanesulfonamide.

[0224] The corresponding acids were obtained by ether extraction ofacidified aqueous solutions of various potassium salts. Lithium saltswere obtained by treating different acids with lithium carbonate Li₂CO₃.

[0225] These salts may be homo- or copolymerized by free radicalinitiated polymerization.

[0226] A porous textile made from GORE-TEX® with a thickness of 100 μm,commercialized by Gore, was impregnated with a concentrated solution oftrifluoromethane-sulfonyl(3-(1,1,2-trifluorovinyloxy)-benzene-sulfonyl)imideoxide in dichloromethane containing cyanovaleric acid as polymerizationinitiator. After evaporation of the solvent, the acid washomopolymerized within the textile matrix by increasing the temperatureof the product under argon to 60° C. during 24 hours. The membrane thusobtained was used as electrolyte in a test cell of a polymer electrolytebattery with combustible hydrogen/oxygen. The life span obtained withthis membrane was longer than 1,000 hours, with good power performances.This membrane may also be used for the Friedel-Crafts heterogeneouscatalysis of the acylation reaction of toluene with benzoyl chloride.

EXAMPLE 24 2,2-Fluorovinylsulfonyl(Trifluoromethane-Sulfonyl)Imide

[0227] Under argon, to a solution of 6.02 g (20 mmoles) of the lithiumsalt of trifluoromethane-sulfonyl(2,2,2-trifluoroethanesulfonyl)imideobtained in Example 9, in 40 ml of anhydrous tetrahydrofurane at −20°C., there was slowly added 10 ml of a 2 M solution of butyllithium incyclohexane C₄H₉Li (20 mmoles, commercially available from Aldrich).After 2 hours at −20° C., the reaction mixture was centrifuged to removethe precipitate of lithium fluoride which has appeared during thereaction. After evaporation of the solvents and drying, the lithium saltof 2,2-fluorovinylsulfonyl(trifluoro-methanesulfonyl)imide having apurity determined by a proton and fluorine RMN higher than 99% wasrecovered with quantitative yield.

[0228] Microanalysis has given: H 0.47 (0.36); Li 2.71 (2.47); C 12.51(12.82); N 4.72 (4.98); F 33.54 (33.79); S 22.65 (22.81).

[0229] This salt may be homo- or copolymerized by a free radicalinitiated polymerization.

[0230] The homopolymer prepared by polymerization in anhydroustetrahydrofurane at 66° C., initiated by free radical with1,1′-azobis(cyclohexane-carbonitrile), is soluble in the usual organicsolvents (tetrahydrofurane, acetonitrile, dimethylformamide, ethylacetate, glymes, . . . ) and in aprotic solvating polymers such as poly(ethylene oxide). In an aqueous solution at 25° C., it has aconductivity of 9.3×10⁻³ S.cm⁻¹ at a concentration of 0.5 M. It givesantistatic properties to coatings containing same.

EXAMPLE 25 Dimethylaminosulfonyl(Trifluoromethanesulfonyl)Imide

[0231] To a solution at 0° C. and under argon of 14.36 g (100 mmoles) ofsulfamoyl chloride (CH₃)₂NSO₂Cl (commercially available from Aldrich)and 14.91 g of trifluoromethanesulfonamide CF₃SO₂NH₂ (100 mmoles) in 60ml of anhydrous tetrahydrofurane, there is added 22.44 g (200 mmoles) ofDABCO in solution in 20 ml of anhydrous tetrahydrofurane at 0° C. After2 hours at 0° C., the reaction was continued during 24 hours at roomtemperature. The precipitate of DABCO hydrochloride was removed byfiltering on a fritted glass of porosity No. 4. Then, there is added4.24 g (100 mmoles) of anhydrous lithium chloride, the reaction mixturewas stirred during 24 hours, and it was again filtered to remove theDABCO hydrochloride formed. After evaporation of tetrahydrofurane anddrying, 25.17 g (96% yield) of the lithium salt oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide Me₂NSO₂NLiSO₂CF₃having a purity characterized by a fluorine and proton RMN higher than99% was recovered.

[0232] Microanalysis has given: H 2.34 (2.31); Li 2.52 (2.65); C 13.96(13.65); N 10.75 (10.69); F 21.25 (21.74); S 24.35 (24.46).

[0233] According to the sane process, the lithium salt ofpentafluoroethanesulfonyl(dimethyl-aminosulfonyl)imide (98% yield) wasprepared from the pentafluoroethanesulfonamide obtained in Example 5.

[0234] These salts have an excellent solubility in the usual organicsolvents (tetrahydrofurane, acetonitrile, dimethylformamide, ethylacetate, glymes, . . . ) and in aprotic solvating polymers such as poly(ethylene oxide). In this latter solvent, at a concentration O/Li 12/1,the lithium salt of trifluoromethanesulfonyl(dimethylaminosulfonyl)imidehas a anionic conductivity of 1.2×10⁻⁴ S.cm⁻¹ at 60° C. The concentratedsolutions of the salts in acetone may be utilized as catalyst forDiels-Alder reactions.

[0235] A lithium-polymer generator was produced by utilizing a metalliclithium anode, an electrolyte made of a terpolymer of ethylene oxide,allylglycidylether and methylglycidylether containing the lithium saltof trifluoromethanesulfonyl(dimethylaminosulfonyl)imide at aconcentration O/Li=20/1, and a composite cathode based on vanadium oxide(40% by volume), carbon black (5% by volume) and an electrolyteidentical to the one described above (50% by volume). This generator hasgiven a cycling profile at 60° C. which is equivalent to the oneobtained by utilizing one of the more currently known salts for thisapplication, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

EXAMPLE 26 Dimethylaminosulfonyl(Trifluoromethanesulfonyl)Imide

[0236] To a solution kept at 0° C. and under argon containing 14.36 g(100 mmoles) of sulfamoyl chloride (CH₃)₂NSO₂Cl (commercially availablefrom Aldrich) and 14.91 g of trifluoromethanesulfonamide CF₃SO₂NH₂ (100mmoles) in 60 ml of anhydrous tetrahydroflurane, there is added 22.44 g(200 mmoles) of DABCO in solution in 20 ml of anhydrous tetrahydrofuraneat 0° C. After 2 hours at 0° C., the reaction was continued during 24hours at room temperature. The precipitate of DABCO hydrochloride wasremoved by filtration on a fritted glass of porosity No. 4. Afterevaporation of tetrahydrofurane and drying, the product was solubilizedin 25 ml of ethanol. There is then added 9.81 g (100 mmoles) ofpotassium acetate CH₃COOK, then the precipitate obtained with ethanolreflux was recrystallized. After cooling, filtration and drying, 24.13 g(82% yield) of the potassium salt oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide Me₂NSO₂NKSO₂CF₃having a purity characterized by a fluorine and proton RMN higher than99% were recovered.

[0237] Microanalysis has given: H 2.21 (2.05); C 12.56 (12.24); N 9.78(9.52); F 19.89 (19.37); S 21.56 (21.79); K 13.11 (13.28).

[0238] By the same process, the potassium salt ofperfluorobutanesulfonyl(dimethyl-aminosulfonyl)imide (85% yield) wasobtained from perfluorobutanesulfonamide obtained in Example 4.

[0239] The potassium salt oftrifluoromethanesulfonyl)-dimethylaminosulfonyl)imide has a meltingpoint of 188° C. It has a conductivity in poly (ethylene oxide) at aconcentration O/K=12/1 at 60° C. of 5.10⁻⁴ S.cm⁻¹.

[0240] The conductivity of a mixture of the potassium salt and thelithium, salt obtained in Example 25, in a ratio K/Li=2/1 and for atotal concentration in alkaline cation O/(Li+K)=14/1 in poly (ethyleneoxide) was also determined. This conductivity is identical to the onedetermined for the potassium salt alone, which indicates a mechanism ofvehicular transport of lithium in the complex electrolyte by the anionswhich thus travel in the form of an anionic complex, which has littleinteraction with the basic solvent. This type of conductivity is veryfavourable to the operation of lithium generators and more particularlypolymer electrolyte generators, since performances during calls forpower are improved.

EXAMPLE 27 Dimethylaminosulfonyl(Trifluoromethanesulfonyl)Imide of2,2′-Azobis (2-Methylpropionamidine)

[0241] 5.89 g (20 mmoles) of the potassium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide Me₂NSO₂NKSO₂CF₃,prepared according to Example 26, were placed in solution in 10 ml ofwater. Under stiring, 2.71 g of 2,2′-azobis(2-methylpropionamidine)hydrochloride [═NC(CH₃)₂C(═NH)NH₂]₂·2 HCl (10 mmoles, commerciallyavailable from Aldrich) in solution in 10 ml of water were added. Thereis immediately formed a precipitate which was collected by filtration.After drying under vacuum at room temperature, 4.36 (96% yield) of2,2′-azobis (2-methylpropionamidine)dimethylaminosulfonyl(trifluoromethanesulfonyl)imide[═NC(CH₃)₂C(═NH)NH₂]₂·2 Me₂NSO₂NHSO₂CF₃ were recovered.

[0242] This salt is a free radical polymerization initiator which issoluble in most usual organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in aproticsolvating polymers, contrary to 2,2′-azobis(2-methylpropionamidine)hydrochloride.

[0243] An acetonitrile solution of 1 part of this initiator and 100parts of a polymer containing ethylenic unsaturations was prepared. Thispolymer was obtained by polycondensation of polyethylene glycol ofmolecular weight 1,000 with 3-chloro-2-chloromethyl-2-propene accordingto the procedure described by Alloin et al. (Solid States Ionics,(1993), 60, 3). The viscous solution obtained was poured on apolypropylene film (PP). After evaporation of the solvent, the polymerfilm of a thickness of 110 μm on PP was stored for one week in a glovebox under argon for drying. Cross-linking was then initiated by raisingthe temperature of the film to 60° C. After 1 night, there is obtained afilm having good mechanical properties and a low rate of substances thatcan be extracted (lower than 1%). The solubility of the initiator usedin the polymer matrix therefore enables to give an efficient andhomogeneous cross-linking. Moreover, this initiator is not volatile,contrary for example to 2,2′-azobisisobutyronitrile, and the quantityadded may be optimized to the best for each type of polymerization.

EXAMPLE 28 Dialkylaminosulfonyl(Trifluoromethanesulfonyl)Imide

[0244] 15.85 g (200 mmoles) of dibutylamine (C₄H₉)₂NH in solution in 50ml of anhydrous tetrahydrofarane were treated with 27.83 g (200 mmoles)of sulfur trioxide complexed with trimethylamine (CH₃)₃N.SO₃. Afterstirring for 24 hours at room temperature, the solvent was evaporatedand the product was reclaimed in 40 ml of methanol. After having added19.63 g (200 mmoles) of potassium acetate CH₃CO₂K and re-crystallizingthe precipitate obtained, there is recovered after filtration and drying32.66 g of the potassium salt of sulfonic acid of dibutylamine(C₄H₉)₂NSO₃K (66% yield). To 12.37 g of this salt (50 mmoles) in 50 mlof tetrahydrofurane at 0° C., 6.35 g (50 mmoles) of oxalyl chlorideClCOCOCl, and after 2 hours at 0° C., 18.72 g (100 mmoles) of thepotassium salt of trifluoromethanesulfonamide CF₃SO₂NHK were addedslowly. The reaction was continued for 48 hours at room temperature, andthe solvent was evaporated and the product obtained was recrystallizedin 50 ml of water. After filtration and drying, 14.38 g of the potassiumsalt of tifluoromethanesulfonyl(dibutyl-aminosulfonyl)imide(C₄H₉)₂NSO₂NKSO₂CF₃ (76% yield) having a purity characterized by aproton and fluorine RMN higher than 99% were recovered.

[0245] Microanalysis has given: H 4.65 (4.79); C 28.23 (28.56); N 7.1(7.4); F 15.52 (15.06); S 16.45 (16.94); K 10.52 (10.33).

[0246] By a similar process, potassium salts of amides carrying adiethyl substituent (C₂H₅)₂NSO₂NKSO₂CF₃ (66% yield) were prepared fromdiethylamine, and amides carrying a di-2-ethylhexyl substituent[C₄H₉—CH(C₂H₅)—CH₂]₂NSO₂NKSO₂CF₃ (70% yield) was prepared fromdi-2-ethylhexylamine, with purities characterized by proton and fluorineRMN higher than 98%.

[0247] By a similar process, the different potassium salts offluorosulfonyl-(dialkylaminosulfonyl)imides were prepared from thefluorosulfonamide obtained in Example 2, the potassium salts ofpentafluoroethanesulfonyl(dialkyl-aminosulfonyl)imides were preparedfrom the pentafluoroethanesulfonamide obtained in Examiner 5 andpotassium salts of perfluorobutanesulfonyl(dialkyl-aminosulfonyl)imides(C₄H₉)₂NSO₂NKSO₂C₄F₉ were prepared from the perfluorobutanesulfonamideobtained in Example 4.

[0248] By ionic exchange in acetone between the potassium salt oftrifluoromethane-sulfonyl(di-2-ethylhexylaminosulfonyl)imide with aninfrared coloring material of the cyanine family,3,3′-diethylthiatricarbocyanine (commercially available from Aldrich)followed by re-precipitation in water, it was possible to obtain afterfiltration and drying the compound 3,3′-diethylthiatricarbo-cyanine ofdi-2-ethylhexylaminosulfonyl(trifluoro-methanesulfonyl)imide.

[0249] This salt is very soluble in low polar solvents such asdichloromethane or methylene chloride as well as in polymer matriceswith low polarity such as methyl polymethacrylate.

[0250] It was also possible to note a very distinct decrease of theaggregation of cationic colouring materials between one another becauseof the “plasticizing” character of the groups di-2-ethylhexylamino,which is an advantage insofar as the phenomenon of aggregation brings awinding of the optical absorption bands which is prejudicial to theprecision of the operation of systems utilizing these colouringmaterials, in particular optical disks for storing information.

EXAMPLE 29 Dimethylaminosulfonyl (Trifluoromethanesulfonyl) ImideImidazolium

[0251] 14.71 g (50 mmoles) of the potassium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide (CH₃)₂NSO₂NKSO₂CF₃prepared according to Example 26, were co-crushed in an agate mortarunder a glove box with 17.27 g (150 mmoles) of ammonium hydrogenosulfateHSO₄NH₄ (commercially available from Aldrich). By sublimation undersecondary vacuum at 80° C., there is recovered on a cold finger after 24hours 11.2 g (87% yield) oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide (CH₃)₂NSO₂NHSO₂CF₃having a purity characterized by a fluorine and proton RMN higher than99%.

[0252] To a solution in 15 ml of ether containing 1.36 g of imidazole(20 mmoles), there is added 5.12 g of this acid (20 mmoles), and after24 hours under stirring, a precipitate formed is recovered by filtrationon a fritted glass of porosity No. 3. After drying, a quantitativeamount of the imidazolium salt oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide was recovered.

[0253] A crushing under a glove box of a molar mixture of 7 imidazolesfor 2 imidazolium salts has enabled to give a compound having a meltingtemperature lower than ambient. This molten salt has an elevatedprotonic conductivity which is higher than 10⁻³ S.cm⁻¹ at 60° C. It ispossible to obtain a polymer electrolyte, which is an anhydrous protonicconductor by adding poly (ethylene oxide), preferably of high molecularweight or which can later be cross-linked, to the molten salt withoutdetrimentally affecting the conductivity. These polymer electrolytes areparticularly interesting for the preparation of systems for themodulation of light such as electrochrome glass panes includingelectrochrome systems containing coloring materials.

[0254] There is obtained a membrane which is optically transparent invisible light and having a good mechanical behaviour by utilizing apolymer electrolyte made of 80% by weight of molten salt and 20% byweight of poly (ethylene oxide) of molecular weight M_(w)=5.10⁶. Therewas then produced an electrochrome system under glove box by utilizingthis electrolyte enclosed between a first electrode consisting of thedeposit on a glass plate of a layer of hydrogenated iridium oxideH_(x)IhrO₂ and a conductive sub-layer of tin oxide and a secondelectrode consisting of a layer of tungsten trioxide H_(x)IrO₂ and aconductive sub-layer of tin oxide. This electrochrome led to a variationof the optical absorption from 80% (discolored state) to 30% (coloredstate) and good performances in cycling (more than 20,000 cycles ofcoloring/discoloring).

[0255] An electrochrome was also produced by dissolving twocomplimentary coloring materials in such a molten salt: in a glove box,1.62 g (5 mmoles) of the imidazolium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide and 1.02 g ofimidazole (15 mmoles) were crushed together. Then, to the molten salt,there was added 16.5 mg (50 μmoles) of green leucomalachite (colorlessreduced state) and 29.5 mg (50 μmoles) of the salt of3-(4,5-dimethyl-thiazolyl-2-yl)-2,5-diphenyl-2H-tetrazolium (MTT) andtrifluoromethanesulfonyl(dimethyl-aminosulfonyl)imide (colorlessoxidized state, obtained by ionic exchange in water starting from thebromide.). Then, there was added 5% by weight of poly (ethylene oxide)of molecular weight M_(w)=3.10⁵. The salt obtained was placed between 2glass plates covered with a conductive layer of tin oxide (SnO₂). Afterpressing under vacuum to homogenize the deposit and sealing it to makeit impervious, there is obtained a coloring material base electrochromesystem. After having sealed the product obtained to make it impervious,a potential of 1,300 mV was applied on the outside by means of apotentiostat. The system then became colored, and the oxidized form ofgreen malachite and the reduced form of MTT each has an intenseabsorption band in the visible range. By applying a potential of −500mV, a relatively rapid discoloring of the system (lower than 60 s) wasnoted. Such an electrochrome system is easy to prepare, even for systemsof large sizes (higher than m²) which utilize glass or a suitablytreated polymer as conductive transparent electrode. Moreover, theenergy which is necessary to maintain coloration is relatively low,lower than 1 W/m².

EXAMPLE 30 EXAMPLE 30Dimethylaminosulfonyl(Trifluoromethanesulfonyl)Imide

[0256] To-2.56 g oftrifluoromethanesulfonyl(dimethyl-aminosulfonyl)imide (CH₃)₂NSO₂NHSO₂CF₃(10 mmoles), obtained as in Example 29, in solution in 10 ml of water,there is added 763 mg (1.67 mmoles) of anhydrous lanthanum carbonateLa₂(CO₃)₂. After stirring overnight, water was evaporated and thelanthanum salt of trifluoromethanesulfonyl(dimethylaminosulfonyl)-imideCH₃)₂NSO₂NSO₂CF₃]₃ La was recovered in quantitative yield after drying.

[0257] This salt is highly soluble in the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) It is also capable of interaction with solvents with lowpolarities such as dichloromethane, which interaction is better thanthat of the lanthanum salt of bis(trifluoromethane-sulfonyl)imide. Itmay be used as a catalyst in Diels-Alder reactions.

EXAMPLE 31 Dialkylaminosulfonyl(Trifluoromethanesulfonyl)Imide

[0258] To 3.78 g (10 mmoles) of the potassium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)ide (CH₃)₂NSO₂NKSO₂CF₃,obtained in Example 26, in solution in 10 ml of anhydrous nitromethane,there is added in a glove box, 1.17 g of nitrosonium tetra-fluoroborateNOBF₄ (10 mmoles, commercially available from Aldrich). After 1 hour,the reaction mixture was filtered to remove the insoluble potassiumtetrafluoroborate, and there is thus obtained a solution 1 M oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide(CH₃)₂NSO₂N(NO)SO₂CF₃ in nitromethane.

[0259] By a similar process, a 1 M solution in nitromethane of thenitrosonium salt of trifluoromethanesulfonyl(dibutyl-aminosulfonyl)imide(C₄H₉)₂NSO₂N(NO)SO₂CF₃, was prepared from the potassium salt oftrifluoromethanesulfonyl-(dibutylaminosulfonyl)imide (obtained inExample 28) and another 1 M solution in nitromethane of the nitrosoniumsalt of trifluoromethane-sulfonyl(N,N-di-2-ethylhexylaminosulfonyl)imide(C₄H₉CH(C₂H₅)CH₂)₂N(NO)SO₂CF₃, was prepared from the potassium salt oftrifluoromethanesulfonyl-(N,N-di-2-ethylhexylaminosulfonyl)imide(obtained in Example 28).

[0260] These salts are particularly interesting for doping conjugatedpolymers (polythiophene, polypyrrole, . . . ) to which they give anotable electronic conductivity.

[0261] Three deposits of stereoregular poly(3-hexyl-thiophene)(commercially available from Aldrich) were prepared on glass plates froma chloroform solution. After drying, these deposits were doped with oneof the salts in solution in nitromethane. After doping, the threepoly(3-hexylthiophene) films had an electronic conductivity higher than1 S.cm⁻¹ independently of the doping salt. Stability in humid medium ofthe conductivity was improved with an increase of the length of thealkyl segments. These deposits are useful for preparing masks in thesemi-conductor industry.

EXAMPLE 32 Dialkylaminosulfonyl(Trifluoromethanesulfonyl)Imide

[0262] 5.96 g (40 mmoles) of trifluoromethane-sulfonamide CF₃SO₂NH₂ and9.9 ml of pyridine in 60 ml of anhydrous dichloromethane were cooled at−20° C. 5.4 g (40 mmoles) of sulfuryl chloride SO₂Cl₂ diluted in 10 mlof anhydrous dichloromethane and 8.1 g (80 mmoles) of dipropylamine(C₃H₇)₂NH were then added drop-wise. The mixture was stirred for 1 hourat −20° C. and during 24 hours at room temperature. The reaction mixturewas then filtered, and the solvent was evaporated. The product which wasrecovered was reclaimed in 50 ml of water, acidified at a pH 2 with asolution of hydrochloric acid 4 M, the aqueous phase was extracted twicewith 20 ml of ether, the organic phase was dried with magnesium sulfate,and ether was evaporated. After sublimation of the compound obtainedunder secondary vacuum at 40° C., 10 g oftrifluoromethanesulfonyl(dipropylaminosulfonyl)imide (80% yield) havinga purity characterized by a fluorine and proton RMN higher than 98% wererecovered.

[0263] The lithium salt was prepared by pH-metry dosing the acid insolution in water with a titrated solution of lithium hydroxide. Afterevaporating water and drying under vacuum at 60° C. during 24 hours, thelithium salt of trifluoromethanesulfonyl(dipropylaminosulfonyl)-imide(C₃H₇)₂NSO₂NLiSO₂CF₃ was recovered in quantitative yield in the form ofa white powder.

[0264] Microanalysis has given: H 4.33 (4.43); Li 2.01 (2.18); C 26.59 5(26.42); N 8.69 (8.8); F 17.33 (17.91); S 20.46 (20.15).

[0265] According to the same process, the lithium salt oftrifuoromethanesulfonyl(N-methyl-N-ethylaminosulfonyl)imideCH₃(C₂H₅)NSO₂NLiSO₂CF₃ was prepared by the same process and it has apurity determined by a proton and fluorine RMN higher than 99% with ayield of 76%.

[0266] These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide).

[0267] The lithium salt oftrifluoromethanesulfonyl-(dipropylaminosulfonyl)imide has a conductivityof 1.4×10⁻⁴ S.cm⁻¹ in poly (ethylene oxide) at a concentration O/Li=12/1and the cationic transport number is 0.42.

[0268] EXAMPLE 33

3-(Trifluoromethyl)Phenyl(Trifluoromethane-Sulfonyl)Amide

[0269] To 48.34 g of 3-(trifluoromethyl)aniline (300 mmoles) in 250 mlof anhydrous dichloromethane at 0° C., there is added drop-wise during 2hours, 28.21 g of trifluoromethanesulfonic anhydride (CF₃SO₂)20 (100mmoles) diluted in 100 ml of anhydrous dichloromethane, and the reactionwas continued during 24 hours at room temperature. After evaporation ofdichloromethane, the product obtained was reclaimed in 300 ml of water,then acidified with 25 ml of a 4 M solution of hydrochloric acid. Theaqueous solution was then extracted by means of three fractions of 50 mlof ether, the organic phases were combined and dried with magnesiumsulfate. After evaporation of ether and drying, the product obtained waspurified by sublimation under secondary vacuum at 40° C. After 24 hours,25 g of trifluoromethanesulfonyl(3-(trifluoromethyl)phenyl)amidem-CF₃C₆H₄NHSO₂CF₃ (85% yield) were recovered on a cold finger in theform of a white solid crystalline product having a purity characterizedby a fluorine and proton RMN higher than 99%.

[0270] Microanalysis has given: H 1.65 (1.72); C 32.53 (32.77); N 4.62(4.78); F 38.12 (38.88); S 10.72 (10.94).

[0271] The lithium salt was prepared by treating the acid obtained withlithium phosphate Li₃PO₄ during 48 hours in acetonitrile. Afterfiltration of the reaction mixture, evaporation of the solvent anddrying under vacuum at 60° C. during 24 hours, the lithium salt oftrifluoromethanesulfonyl(3-(trifluoromethyl)phenyl) amidem-CF₃C₆H₄NLiSO₂CF₃ was obtained in quantitative yield.

[0272] Sodium and potassium salts were obtained by a similar process,while replacing lithium phosphate respectively with sodium and potassiumphosphate.

[0273] In the same manner,trifluoromethanesulfonyl(3-5-bis(trifluoromethyl)-phenyl)amide (I) wasprepared from 3-5-bis(trifluoro-methyl)aniline,trifuoromethanesulfonyl(4-tri-fluoromethoxy)phenyl)amide (II) wasprepared from trifluoromethanesulfonyl(4-trifluoromethoxy)aniline,trifluoromethanesulfonyl(4-aminopyridine)amide (III) was prepared from4-aminopyridine and trifluoromethanesulfonyl(2,2,2-trifluoroethyl)amide(IV) was prepared from 2,2,2-trifluoroethylamine, as well ascorresponding lithium, sodium and potassium salts.

[0274] For all these salts, derivatives of the type fluorosulfonyl wereobtained by utilizing fluorosulfonic anhydride (FSO₂)₂O (commerciallyavailable from SST Corporation) instead of trifluoromethanesulfonicanhydride.

[0275] These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). They have an oxidation potential higher than 4 V towards alithium anode. The salts of lithium or potassium, or mixtures thereof,may therefore be used for preparing electrolytes (liquids, gels orpolymers) for lithium batteries which utilize a cathode material havinga potential of end of recharge lower than 4 V (TiS₂, V₂O₅, Fe(PO₄)₂).Tin salts (II) may be used for catalyzing aldolic condensations.

EXAMPLE 34 Trifluoro-Methane-Sulfonyl(2-Trifluoromethyl-1,3,4-Thiadiazole5-Amino)Amide

[0276] By operating in a glove box under argon, to 16.91 g (100 mmoles)of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole (commercially availablefrom Aldrich) in solution in 100 ml of anhydrous tetrahydrofurane at−30° C., there is added drop-wise 100 ml of a 1 M solution ofdibutylmagnesium (C₄H₉)₂Mg (100 mmoles, commercially available fromAldrich) in heptane. After 4 hours at −30° C., 16.85 g (100 mmoles) oftrifluoromethanesulfonyl chloride CF₃SO₂Cl were added slowly. Thereaction is continued during 2 hours at −30° C., then for 24 hours atroom temperature. The solvents were then evaporated, the product wasreclaimed in water and extracted with ether after acidifying the aqueoussolution. The compound obtained after evaporation of ether wassublimated under secondary vacuum at 40° C., and 25.73 g oftrifluoromethanesulfonyl(5-trifluoromethyl-1,3,4-thiadiazole)amide (86%yield) were thus recovered on a cold finger after 24 hours.

[0277] Microanalysis has given: H 0.39 (0.33); C 15.29 (15.95); N 13.28(13.95); F 38.3 (37.85); S 20.62 (21.29).

[0278] The lithium salt was obtained by treating the acid with lithiumcarbonate Li₂CO₃ in water.

[0279] This salt is soluble in most usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide).

[0280] This salt has an oxidation potential in a mixture of ethylenecarbonate and dimethylcarbonate (2:1), at a concentration of 1 M, higherthan 4V towards a lithium anode.

EXAMPLE 35 Trifluoro-Methane-Sulfonyl(2-Trifluoromethyl-Thiadiazole-5-Aminosulfonyl)Imide

[0281] First, 5-trifluoromethyl-2,3,4-thiadiazole-2-sulfonyl chloridewas prepared from 2-amino-trifluoromethyl-1,3,4-thiadiazole(commercially available from Aldrich), following the procedure describedin Example 7.

[0282] Then, by a procedure similar to the one used in Example 25 forthe synthesis of the lithium salt ofdimethylaminosulfonyl(trifluoromethanesulfonyl)imide, the lithium saltoftrifluoromethanesulfonyl(5-trifluoromethyl-1,3,4-thiadiazole-5-sulfonyl)imidewas synthesized. The product obtained has a purity determined by protonand fluorine RMN higher than 98%.

[0283] Microanalysis has given: Li 1.36 (1.9); C 13.29 (12.9); N 11.88(11.3); F 31.4 (30.7); S 26.46 (25.9).

[0284] This salt is soluble in most usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide).

[0285] This salt has an oxidation potential, at a concentration of 0.5 Min acetonitrile, higher than 4.5 V towards a lithium anode. It may beused for Li-Ion batteries with liquid or gel electrolytes. Thus, abattery was assembled by utilizing an anode consisting of coke carbon(80% by volume) mixed with vinylidene polyfluoride (PVDF, commerciallyavailable from Montedison) as binder (20% by volume), an electrolytecompound of a mixture of ethylene carbonate and dimethylcarbonate (2:1),gelled with PVDF, containing this salt at a concentration of 1 M and acomposite cathode consisting of carbon black (6% by volume), Li₂MnO₄(75% by volume) and PVDF as binder (20% by volume). This generator hasgiven good performances in cycling at 25° C. (1,000 cycles ofcharge/discharge between 2 and 4.7 V by maintaining about 50% of thecapacity at the first cycle).

EXAMPLE 36Trifluoro-Methane-Sulfonyl(2-Trifluoromethyl-Thiadiazole-5-Aminosulfonyl)Amide

[0286] In 20 ml of anhydrous acetonitrile under stirring, 2.29 g (10mmoles) of trichloromelamine (commercially available from Fluka) weretreated with 5.16 g of potassium triflinate in the presence of 6.37 g ofpotassium phosphate K₃PO₄ (30 mmoles). After 72 hours under stirring,the solvent was evaporated and the residue was recrystallized in 40 mlof water. After filtration and drying, 10.69 g (56% yield) of apotassium trisalt oftris-[1,3,5-trifluoromethanesulfonamide]-2,4,6-tri-azine with a puritydetermined by a proton and fluorine RMN higher than 99%.

[0287] Microanalysis has given: C 11.52 (11.32); N 13.61 (13.2); F 26.99(26.86); S 15.01 (15.11); K 18.21 (18.43).

[0288] The trisalt of lithium was obtained by ionic exchange withlithium chloride LiCl in tetrahydrofurane.

[0289] The lithium salt is soluble in most of the usual organic solvents(tetrahydroflurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). In this latter solvent containing the lithium salt at aconcentration O/Li=12/1, the cationic transport number is 0.52 at 60° C.

[0290] The tri-salt of tetrabutylammonium was obtained by treatment ofthe lithium tri-salt with tetrabutylammonium chloride (5% in excess) inwater. The precipitate obtained was thereafter recovered by extractionwith dichloromethane, the dichloromethane solution was washed withwater, and evaporated. The tri-salttris-[1,3,5-trifluoromethanesulfonamide]-2,4,6-triazinetri-tetrabutylammonium was recovered in quantitative yield. An additionof 3.5% by weight of this compound to a poly(acrylonitrile-co-butadiene)copolymer containing 20% by weight of acrylonitrile gives antistaticproperties to the copolymer.

EXAMPLE 37Trifluoromethanesulfonyl(1,1,1,3,3,3-Hexafluoro-2-Propanoxysulfonyl)Imide

[0291] 5.96 g (40 mmoles) of trifluoromethanesulfonamide CF₃SO₂NH₂ and9.9 ml of pyridine in 60 ml of anhydrous dichloromethane were cooled to−15° C. 5.4 g (40 mmoles) of sulfuryl chloride SO₂Cl₂ diluted in 10 mlof anhydrous dichloromethane were added drop-wise, and this was followedby 6.72 g (40 mmoles) of 1,1,1,3,3,3-hexafluoro-2-propanol (CF₃)₂CHOH.The mixture was stirred for 1 hour at −15° C., and during 12 hours atroom temperature. The reaction mixture was thereafter filtered, and thesolvent was evaporated. The product which was recovered was reclaimed in50 ml of water, acidified with 10 ml of a hydrochloric acid solution 4M; the aqueous phase was extracted twice with 20 ml of ether, theorganic phase was dried with magnesium sulfate and ether was evaporatedby means of a rotary evaporator. After sublimation under secondaryvacuum at 40° C. of the compound obtained, 13.9 g oftrifluoromethanesulfonyl-(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide(92% yield) having a purity characterized by a fluorine and proton RMNhigher than 98% were recovered.

[0292] Microanalysis has given: H 0.46 (0.53); C 12.35 (12.67); N 3.76(3.69); F 44.3 (45.09); S 16.23 (16.91).

[0293] An aqueous solution of the lithium salt was obtained by treatingthe acid with lithium carbonate Li₂CO₃ in water. Then, by addition of1-ethyl-3-methyl-1H-imidazolium chloride (10% in excess, commerciallyavailable from Aldrich), a liquid phase of higher density than water wasobtained. This phase was recovered by extraction with dichloromethane.After evaporation of dichloromethane and drying under vacuum at 40° C.of the liquid obtained, the molten salt of trifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide1-ethyl-3-methyl-1H-imidazolium was recovered (91% yield).

[0294] This molten salt has a conductivity of 3.91×10⁻³ S.cm⁻¹ and afreezing point lower than −20° C. Its large range of redox stabilityenables it to be a particularly interesting electrolyte forelectrochemical generators such as lithium batteries, supercapacitances,systems for modulating light and photovoltaic cells.

[0295] An electrochemical photovoltaic cell was prepared by assembling asystem made of two electrodes separated by a vacuum space 30 μm thick.The first electrode was coated with a layer of nanoparticles of titaniumdioxide TiO₂ 0.25 μm thick on which the1,3-phenylsulfonamide-N,N′-trifluoro-methanesulfonyl rhodamine Bobtained in Example 25 was adsorbed as a sensitizer. The space betweenthe electrodes was filled with an electrolyte made of the molten salt inwhich 10% by weight of methylhexylimidazolium and 10 mmoles of iodinewere solubilized. The short circuit current of this cell is 103 μA.cm⁻²and its voltage in open circuit was 552 mV.

EXAMPLE 38 Cyano(Perfluorobutanesulfonyl)Imide

[0296] To 5.16 g (60 mmoles) of cyanamide di-sodium (commerciallyavailable from Aldrich) in 30 ml of dimethoxyethane at 0° C., there isadded 15.1 g of perfluorobutanesulfonyl fluoride (50 mmoles) at 0° C.After 3 hours at 0° C., and 24 hours at room temperature, the reactionmixture was centrifuged and filtered to remove the excess of cyanamideand the sodium fluoride formed. The product obtained was reclaimed in 20ml of methanol after evaporation of dimethoxyethane, and 4.91 g ofanhydrous potassium acetate CH₃COOK (50 mmoles) were added. Theprecipitate which was formed is recrystallized, and recovered byfiltration. After drying, 12.5 g of potassium perfluorobutanesulfonyl(cyano)imide C₄F₉SO₂NKCN (69% yield) were obtained in the form of awhite powder having a purity characterized by a fluorine and proton RMNhigher than 97%.

[0297] Microanalysis has given: C 16.18 (16.58); N 7.23 (7.73); F 47.98(47.21); S 8.12 (8.85); K 11.2 (10.79).

[0298] In the same manner, potassium salts of cyano(fluorosulfonyl)imide(I) were prepared from fluorosulfonyl chloride ClSO₂F,cyano(trifluoromethanesulfonyl)imide (II) was prepared fromtrifluoromethanesulfonyl chloride CF₃SO₂Cl andcyano(pentafluoroethanesulfonyl)imide (III) was prepared frompentafluoroethanesulfonyl chloride C₂F₅SO₂Cl.

[0299] The lithium salts were prepared in quantitative yield by ionicexchange between the potassium salt and lithium chloride in anhydroustetrahydrofurane.

[0300] These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). In this latter solvent, it has a conductivity higher than 2×10⁻⁴S.cm⁻¹ at 60° C. for a concentration O/Li=12/1.

[0301] An electrochemical supercapacitance was prepared by utilizing a 1M solution of each of the above potassium salts in acetonitrile aselectrolytes and carbon/aluminum composites as electrodes. For eachsupercapacitance, the electrodes with a thickness of 150 μm were placedon both sides of a microporous polyethylene 40 μm thick impregnated witha potassium salt and the complete system was sealed in a glove box in abutton shaped battery housing. Good performances were obtained withthese supercapacitances (more than 100,000 cycles of charge/dischargebetween 0 and 2.5 V for a density of energy higher than 25 Wh/l and adelivered power higher than 1,500 W/l.

EXAMPLE 39 Alkylsulfonyl(Trifluoromethanesulfonyl)Imide

[0302] 7.83 g (50 mmoles) of butanesulfonyl chloride C₄H₉SO₂Cl insolution in 30 ml of anhydrous tetrahydrofurane at 0° C. were treatedwith 17.11 g (100 mmoles) of sodium trifluoromethanesulfonamideCF₃SO₂NHNa. After 1 hour at 0° C., and 24 hours at room temperature, thesolvent was evaporated and the product was reclaimed in 50 ml of water.An addition of 3.73 g of anhydrous potassium chloride KCl (50 mmoles)resulted in the appearance of a precipitate which was recrystallized,and recovered by filtration and finally dried. 9.37 g of potassiumtrifluoromethanesulfonyl(butanesulfonyl)imide (61% yield)C₄H₉SO₂NKSO₂CF₃ were thus obtained in the form of a crystallized whitepowder, having a purity determined by a fluorine and proton RMN higherthan 99%.

[0303] Microanalysis has given: H 2.75 (2.95); C 19.01 (19.54); N 4.98(4.56); F 18.21(18.54); S 20.25 (20.86); K 12.56 (12.72).

[0304] Potassium trifluoromethanesulfonyl(octylsulfonyl)imide (I) andpotassium trifluoromethanesulfonyl(dodecylsulfonyl) ride (II) wereobtained under identical conditions respectively from octylsulfonylchloride and dodecylsulfonyl chloride.

[0305] The lithium salts of these three derivatives were prepared inquantitative yield by ionic exchange between the potassium salt andlithium chloride in anhydrous tetrahydrofurane. The lithium salt oftrifluoromethanesulfonyl(dodecylsulfonyl)imide dissolved in a matrix ofpoly (ethylene oxide) at a concentration O/Li=16/1 has a cationictransport number of about 0.55. The result is that when this compound isused as an electrolyte in a polymer electrolyte lithium battery, thegradients of concentration which appear during the operation of thebattery are decreased substantially. Performances during calls for powerare thus improved.

EXAMPLE 40 Octylsulfonyl(Fluorosulfonyl)Imide

[0306] 5.16 g (25 mmoles) of octylsulfonyl chloride C₈H₁₇SO₂Cl insolution in 20 ml of anhydrous tetrahydrofurane at 0° C. were treatedwith 6.86 g (50 mmoles) of potassium fluorosulfonamide. After 1 hour at0° C. and 24 hours at room temperature, the solvent was evaporated andthe product was recrystallized in 15 ml of water. After filtration anddrying, 5.64 g of potassium fluorosulfonyl(butanesulfonyl) imideC₈H₁₇SO₂NKSO₂F (72% yield) having a purity determined by a fluorine andproton RMN higher than 99% was recovered. The lithium salt was preparedby ionic exchange (metathesis) between the potassium salt and lithiumchloride in anhydrous tetrahydrofurane.

[0307] Microanalysis has given: H 5.27 (5.47); C 30.98 (30.66); N 4.78(4.47); F 6.52 (6.06); S 20.96 (20.46); K 12.01 (12.47).

[0308] The lanthanum salt of fluorosulfonyl(butanesulfonyl)imideC₈H₁₇SO₂NKSO₂F may be used as catalyst for Diels-Alder reactions, inparticular in dichloromethane.

[0309] These salts possess plasticizing properties.

EXAMPLE 41 Triisopropylsulfonyl(Fluorosulfonyl)Imide

[0310] 3.96 g of fluorosulfonamide FSO₂NH₂ (40 mmoles) and 12.11 g of2,4,6-triisopropylbenzenesulfonyl chloride (40 mmoles, commerciallyavailable from Aldrich), were stirred in 40 ml of anhydroustetrahydroflurane at 0° C. in the presence of 8.49 g of anhydrouspotassium phosphate K₃PO₄. After 3 hours at 0° C., and 48 hours at roomtemperature, the solvent was evaporated and the product was reclaimed in24 ml of cold water. The addition of 2.98 g of anhydrous potassiumchloride gave a precipitate which was recrystallized, recovered byfiltration, and dried. There is thus obtained 11.78 g of potassiumfluorosulfonyl fluorosulfonyl (2,4,6-triisopropyl-benzenesulfonyl)imide(73% yield) having a purity determined by a fluorine and proton RMNhigher than 98%.

[0311] Microanalysis has given: H 5.58 (5.98); C 44.14 (44.53); N 3.78(3.46); F 5.02 (4.7); S 15.23 (15.85); K 10.21 (9.66).

[0312] The lithium salt was prepared by ionic exchange (metathesis)between the potassium salt and lithium chloride in anhydroustetrahydrofurane.

EXAMPLE 421-Dodecyl-1,1,1,3,3,3-Hexafluoro-2-Propanoxysulfonyl(Trifluoromethanesulfonyl)Imide

[0313] By operating in a glove box under argon, 18.96 g (50 mmoles) oftrifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxy-sulfonyl)imideprepared as in Example 37, were placed in solution in 20 ml of anhydroustetrahydrofurane. After having brought this solution to −20° C., 10 mlof a 1 M solution of potassium tert-butoxide (CH₃)₃COK (100 mmoles,commercially available from Aldrich) in tetrahydrofurane were addedslowly. After 15 minutes, 12.46 g of 1-bromododecane (50 mmoles) wereadded. The reaction is continued for 2 hours at −20° C., then during 24hours at room temperature. After 48 hours, the solvent was evaporatedand the residue was recrystallized in 50 ml of water containing 7.46 g(100 mmoles) of potassium chloride KCl. After filtration and drying,there is obtained potassium 1-dodecyl-1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl-(trifluoromethanesulfonyl)imideof a purity characterized by a proton and fluorine RMN higher than 99%.

[0314] Microanalysis has given: H 4.8 (4.5); C 34.5 (34.1); N 2.8 (2.3);F 28.1 (28.5); S 10.1(10.7); K 6.1 (6.5).

[0315] The lithium salt was obtained in quantitative yield by treatingthe potassium salt in anhydrous tetrahydrofurane by a stoichiometricquantity of anhydrous lithium chloride, filtration of the reactionmixture, evaporation of the solvent and drying under vacuum.

[0316] These salts may be used as additives for laminating lithium andfor the extrusion of polymers, in particular the extrusion of poly(ethylene oxide). They have plasticizing properties.

EXAMPLE 43 Igepal® CA-520-Propylsulfonyl(Trifluoromethanesulfonyl)Imide

[0317] In 30 ml of tetrahydrofurane, 4.27 g of Igepa® CA-520 (10 mmoles,commercially available from Aldrich) were treated with 3.28 (10 mmoles)of trifuoromethanesulfonyl(3-chloropropanesulfonyl)-imide obtained as inExample 8, in the presence of 4.24 g of potassium phosphate K₃PO₄ (20mmoles). After 72 hours under stirring at 60° C., the reaction mixturewas filtered so as to remove potassium phosphate and potassium chlorideformed during the reaction. After evaporation of the solvent and drying,7.18 g of potassium Igepal®CA-520-propyl-sulfonyl(trifuoromethanesulfonyl)imide having a puritydetermined by proton and fluorine RMN higher than 96% were recovered.

[0318] Microanalysis has given: H 6.89 (6.6); C 46.45 (46.85); N 1.69(1.95); F 7.66 (7.94); S 8.72 (8.93); K 5.75 (5.45).

[0319] This salt is an excellent additive for the extrusion of poly(ethylene oxide). It also enables to plasticize a large number ofpolymers containing polar units (ether, amide, nitrile, ester . . . ),while giving them a high ionic conductivity.

EXAMPLE 44 Toluenesulfonyl(Trifluoromethanesulfonyl)Imide

[0320] By operating in a glove box under argon, 3.23 g ofdichlorotriphenylphosphorane (C₆H₅)₃PC₁₂ (10 mmoles) were added byportions to a solution of 2.24 g (20 mmoles) of DABCO and 1.49 g oftrifluoromethanesulfonamide CF₃SO₂NH₂ (10 mmoles) in 20 ml ofacetonitrile. After 3 hours under stirring, the reaction mixture wasfiltered to remove the precipitate of DABCO chloride formed, and thesolvent was evaporated. There was recovered a quantitative yield oftriphenylphosphoranylidene-sulfonyl-trifluoromethyl CF₃SO₂N═P(C₆H₅)₃ inquantitative yield. Then, this compound was reacted with 1.94 g (10mmoles) of the sodium salt of p-toluenesulfonic acid in 10 ml ofdimethylformamide at 60° C. After 48 hours under stirring, the solventwas evaporated and the residue was recrystallized in 10 ml of watercontaining 1 g of potassium chloride KCl. After filtration and drying,2.46 g of sodium p-toluenesulfonyl(trifluoromethanesulfonyl)imide (76%yield) having a purity determined by a proton and fluorine RMN higherthan 99% were recovered.

[0321] Microanalysis has given: H 2.07 (2.17); C 29.88 (29.54); N 4.01(4.31); F 17.23 (17.52); Na 7.15 (7.07); S 19.21 (19.71).

EXAMPLE 45O,O′-[Propylsulfonyl-(Trifluoromethanesulfonyl)Imide]Polyethylene Glycol

[0322] A sulfonated oligomer of poly (ethylene oxide) was prepared asfollows: 12 g of poly(ethylene glycol) of molecular weight 600 (≈40mmoles of hydroxyl functions) were dried by azeotropic distillation withbenzene and by lyophilization. After addition of 50 ml of anhydroustetrahydrofurane, the terminal hydroxyl groups were metal substitutedwith potassium-naphthalene. The stoichiometry was determined bycolorimetry, and the end of the reaction was is indicated by apersistence of an intense green color of the anion radical ofnaphthalene. Then, 4.89 g of 1,3-propane sultone (40 mmoles) were added.After evaporation of the solvent, the α,ω-disulfonated polymer wasobtained in the form of powder and the residual naphthalene was removedby washing with hexane. 8.44 g of the product thus formed (≈20 mmoles of—SO₃H), in suspension in 20 ml of anhydrous acetonitrile, were treatedwith 2.82 g of (chloromethylene)dimethylammonium chloride[(CH₃)₂N═CHCl]⁺, Cl⁻ (22 mmoles, commercially available from Aldrich). Aprecipitate of potassium chloride was formed after about 1 h. 3.28 g oftrifluoromethanesulfonamide (22 mmoles) and 2.47 g of DABCO (22 mmoles)were added to this suspension. After filtration, the reaction mixturewas stirred in the presence of 3.4 g of lithium phosphate Li₃PO₄ during24 hours. A new filtration followed by a reprecipitation in 200 ml etherat 0° C. has enabled to recover a viscous fluid which is very lightlycolored, characterized by a proton and fluorine RMN as in the case ofthe di-lithium salt of poly(ethylene glycol)α,ω-trifluoromethanesulfonyl-(propanesulfonyl)imide:

[0323] This salt is soluble in most polar organic solvents(acetonitrile, tetrahydrofurane, DMF, . . . ) and it may be used toplasticize a large number of polymers containing polar units (ether,amide, nitrile, ester . . . ), while giving them a high ionicconductivity.

EXAMPLE 46Trifluoromethanesulfonyl(R(−)-1-phenyl-2,2,2-Trifluoroethanoxysulfonyl)Imide

[0324] 5.96 g (40 mmoles) of trifluoromethanesulfonamide and 9.9 ml ofpyridine in 60 ml of anhydrous dichloromethane were cooled to −15° C.0.4 g (40 mmoles) of sulfuryl chloride diluted in 10 ml of anhydrousdichloromethane were then added drop-wise, followed by 7.05 g (40mmoles) of R(−)-1-phenyl-2,2,2-trifluoroethanol (commercially availablefrom Fluka). The mixture was stirred for 1 hour at −15° C., and for 4hours at room temperature (25° C.) The reaction mixture was filtered andthe solvent was removed with a rotary evaporator. The product which wasrecovered was reclaimed in 20 ml of ethanol. A precipitate is formedafter the addition of 3.93 g (40 mmoles) of potassium acetate. Afterrecrystallization, filtration and drying, there is obtained 12.25 g ofpotassiumtrifluoromethanesulfonyl(R(−)-1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imide(72% yield) having a purity characterized by a fluorine and proton RMNhigher than 98%.

[0325] Microanalysis has given: H 1.65 (1.42); C 25.21 (25.41); N 3.55(3.29), F 26.21 (26.8); S 15.65 (15.07); K 9.56 (9.19).

[0326] In the same manner, potassiumtrifluoromethanesulfonyl-(S(+)-1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imide(66% yield) was obtained from R(−)-1-phenyl-2,2,2,-trifluoroethanol.Lithium salts were obtained by ionic exchange (metathesis) intetrahydroflurane with lithium chloride.

[0327] Lanthanum salts were obtained by treating potassium salts with astoichiometric quantity of lanthanum perchlorate La(ClO₄)₃,6H₂O in amixture of acetonitrile and isopropyl orthoformate intended to removethe water of crystallization from the salt of lanthanum. Afterfiltration to remove the precipitate of potassium perchlorate KClO₄ andevaporation of the solvent, the lanthanum salts of the two enantiomersoftrifuoromethanesulfonyl-(1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imidewere recovered in quantitative yield.

[0328] These salts are soluble in most polar organic solvents(acetonitrile, tetrahydrofurane, DMF, . . . ) and in aprotic solvatingpolymers.

EXAMPLE 47Trifluoromethanesulfonyl(N-Methoxybutyl-N-2-Butyl-3-Methyl)Aminosulfonyl)Imide

[0329] The two enantiomers of the potassium salt oftrifluoromethanesulfonyl(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)-imidewere obtained by a process similar to the one described in Example 28,from N-methoxybutyl-N-2-butyl-2-methylamine (commercially available fromAir Products) with a purity higher than 99% and a yield of 62%.

[0330] By the same process, potassium salts of the two enantiomers offluorosulfonyl(N-methoxybutyl-N-2-butyl-3-methyl)-aminosulfonyl)imidewere also obtained.

[0331] The lithium salts are obtained by ionic exchange (metathesis) intetrahydrofurane with lithium chloride.

[0332] By a process similar to the one described in Example 46,lanthanum salts of the two enantiomers oftrifluoromethanesulfonyl-(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)-(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)imideand the two enantiomers offluorosulfonyl-(N-methoxybutyl-N-2-butyl-3-methyl)amino-sulfonyl imidewere obtained.

[0333] These salts are soluble in most polar organic solvents(acetonitrile, tetrahydrofurane, DMF, . . . ) and in aprotic solvatingpolymers.

EXAMPLE 48 Camphorsulfonyl(Trifluoromethanesulfonyl)Imide

[0334] According to a process similar to the one described in Example39, the potassium salt of(1R)-(−)-10-camphorsulfonyl(trifluoromethanesulfonyl)imide was obtainedfrom (1R)-(−)-10-camphorsulfonyl (commercially available from Aldrich),and potassium(1S)-(+)-10-camphorsulfonyl(trifluoromethanesulfonyl)-imide was obtainedfrom (1S)-(+)-10-camphorsulfonyl chloride (commercially available fromAldrich) with yields higher than 70%. The purity of the compoundsobtained, determined by proton and fluorine RMN, is higher than 99%.

[0335] The potassium salt of(1r)-(−)-10-camphorsulfonyl(perfluorobutane-sulfonyl)imide and(1S)-(+)-10-camphorsulfonyl(perfluorobutanesulfonyl)imide were obtainedfrom perfluorobutanesulfonamide C₄F₉SO₂NH₂ obtained in Example 4.

[0336] Lithium salts were obtained by ionic exchange (metathesis) intetrahydrofurane with lithium chloride.

[0337] By a process similar to the one described in Example 46,lanthanum salts of (1R)-(−)-10-camphorsulfonyl(perfluorobutane-sulfonyl)de and of (1s)-(+)-10-camphorsulfonyl(perfluorobutanesulfonyl)ide wereobtained:

[0338] These salts are soluble in most polar organic solvents(acetonitrile, tetrahydrofurane, DMF, . . . ) and in aprotic solvatingpolymers.

EXAMPLE 49 N-(1S)-(+)-Ketopinic-Acetylmethylsulfonyl(Trifluoromethanesulfonyl)Imide

[0339] By operating in a glove box under argon, 2.8 g (10 mmoles) of thepotassium salt of trifuoromethanesulfonyl(N-methyl-sulfonyl) imideCF₃SO₂NKSO₂NH(CH₃) obtained in Example 10, in solution in 5 ml ofanhydrous tetrahydrofurane, there is slowly added 10 ml of a 1 Msolution in tetrahydrofurane of potassium tert-butoxide (CH₃)₃COK (10mmoles).

[0340] At the same time, to 1.82 g (10 mmoles) of (1S)-(+)-ketopinicacid (commercially available from Aldrich) in solution in 10 ml ofanhydrous acetonitrile, there is added 80 mg of lithium hydride LiH (10mmoles), and after a few minutes, 1.27 g of oxalyl chloride ClCOCOCl (10mmoles). After centrifugation, the solution of THF was poured into thissolution. The reaction was continued 24 hours at room temperature. Thereaction mixture was then filtered to remove the precipitate ofpotassium chloride, and the solvent was evaporated and the productrecrystallized in 6 ml of water. After filtration and drying, 2.76 g ofpotassiumtrifluoromethanesulfonyl(N-(1S)-(+)-ketopinic-acetyl-N-methyl-sulfonyl)imide(62% yield) were obtained with a purity characterized by a proton andfluorine RMN higher than 99%.

[0341] The scandium salt was obtained by treating the potassium saltwith a stoichiometric quantity of scandium tetrafluoroborate Sc(BF₄)₃ inacetonitrile. After filtration to remove the precipitate of potassiumtetrafluoroborate KBF₄ and evaporation of the solvent, after drying, thescandium salt oftrifluoromethanesulfonyl(N-(1S)-(+)-ketopinic-acetyl-N-methylsulfonyl)idewas recovered in quantitative yield.

EXAMPLE 50 Dialkylaminosulfonyl(Trifluoromethanesulfonyl)ImideDiphenyliodonium

[0342] 1.58 g (5 mmoles) of diphenyliodonium chloride (C₆H₅)₂ICl and1.89 g of potassium trifluoromethanesulfonyl(dibutyl-aminosulfonyl)imide(C₄H₉)₂NSO₂NKSO₂CF₃ (5 mmoles) were stirred together during 24 hours inwater. By extraction of the aqueous phase with dichloromethane, afterevaporation is of dichloromethane and drying, 3.01 g of thediphenyliodonium salt oftrifluoromethanesulfonyl(dibutylaminosulfonyl)imide (97% yield) wereobtained with a purity characterized by a proton and fluorine RMN higherthan 99%.

[0343] By the same process, the diphenyliodonium salt oftrifluoromethanesulfonyl(N,N-di-3-ethylhexyl-aminosulfonyl)imide wasprepared with a yield of 98% and with a purity characterized by a protonand fluorine RMN higher than 99%.

[0344] These salts enable to initiate under the action of actinicradiation (light, γ rays, electron beams) a cationic cross-linkingreaction of monomers rich in electrons (vinyl ethers, alkyl vinylethers).

[0345] They are soluble in most usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). They are also soluble to an extent of 10% by weight in reactivesolvents such as triethyleneglycol divinyl ether. The properties ofphoto-initiation of these salts were tested by irradiating with U.V.radiation at 254 nm, a power of 1,900 mW/cm², a solution oftriethyleneglycol divinyl ether containing same at 1% by weight. After afew seconds under irradiation, the reactive solvent has solidified, thisreaction being very exothermal.

EXAMPLE 51(4-Butoxybenzene)-[Trifluoromethanesulphonyl-(4-Phenylsulfonyl)Imide)]-Iodonium

[0346] To a solution of 4.49 g (40 mmoles) of DABDO and 2.98 g oftrifluoromethanesulfonamide CF₃SO₂NH₂ (20 mmoles), in 10 ml of anhydroustetrahydrofurane at 0° C., there is added 6.05 g of4-iodobenzenesulfonyl chloride IC₆H₄SO₂Cl (20 mmoles, Aldrich) dilutedin 5 ml of anhydrous tetrahydrofurane. After 2 hours at 0° C., thereaction was continued during 24 hours at room temperature. The DABCOhydrochloride formed during the reaction was removed by filtration on afritted glass of porosity No. 4. After evaporation of acetonitrile fromthe filtered solution, the product was reclaimed in 15 ml of cold waterand there was slowly added 1.49 g of anhydrous potassium chloride (20mmoles) in solution in 5 ml of water. A precipitate appeared which wascollected by filtration on a fritted glass of porosity No. 4. Afterdrying, 7.89 g of potassiumtrifluoromethanesulfonyl(4-iodobenzenesulfonyl)imide (87% yield) havinga purity characterized by a proton and fluorine RMN higher than 99% wererecovered.

[0347] This compound was oxidized into CF₃SO₂NKSO₂C₆H₄I(O₂CCH₃)₂(iodosoacetate) with a mixture of acetic acid, acetic anhydride andhydrogen peroxide according to the method of Yamada & al (DieMakromolecular Chemie, (1972), 152, 153-162). 5.71 g of the compoundthus prepared (10 mmoles) were suspended in a mixture of 15 ml ofmethanesulfonic acid and 4.51 g of butoxybenzene (30 mmoles) kept at 0°C. during 4 hours. The reaction product was poured into 300 ml ether andthe precipitate was separated by filtration, washed with ether anddried. There is thus obtained 4.62 g (82% yield) of a zwitterion of(4-butoxybenzene)-[trifluoromethanesulfonyl-(4-phenylsulfonyl)-imide]iodonium [CF₃SO₂N—SO₂C₆H₄I⁺C₆H₄₀C₄H₉] having a purity characterized by aproton and fluorine RMN higher than 97%.

[0348] By a similar process, the compound(4-butoxybenzene)-[pentafluoroethanesulfonyl-4(4-phenylsulfonyl)imide]iodoniumwas obtained from pentafluoroethanesulfonamide and(4-butoxy-benzene)-[perfluorobutanesulfonyl-(4-phenyl-sulfonyl)imide]iodoniumfrom perfluorobutanesulfonamide. These compounds have analogousproperties to those of the compounds of Example 50 and may be used forthe same application.

EXAMPLE 52 Tetrakis(Acetonitrile)Palladium(II)Trifluoromethane-Sulfonyl(N,N-di-2-Ethylhexylaminosulfonyl)Imide

[0349] 2.22 g (5 mmoles) of tetrakis(acetonitrile)palladiumtetra-fluoroborate(II) (CH₃CN)₄Pd(BF₄)₂ (commercially available fromAldrich), in 30 ml of tetrahydrofurane were treated with 4.91 g ofpotassium trifluoromethanesulfonyl(N,N-di-2-ethylhexylaminosulfonyl)ide(10 mmoles) obtained in Example 28. After 24 hours under stirring, thereaction mixture was filtered to remove the precipitate of potassiumtetrafluoroborate KBF₄, and the solvent was evaporated.Trifluoromethanesulfonyl-(N,N-di-2-ethylhexylaminosulfonyl)imide oftetrakis-(acetonitrile)palladium(II) was obtained in quantitative yield.

[0350] This salt is useful as catalyst for the vinyl polymerization ofnorbornene. Thus, norbornene was polymerized at room temperature innitromethane in the presence of 300 ppm of this salt. After 2 hours, thereaction mixture was reprecipitated in methanol. Polynorbornene wasobtained with a number average molecular weight of 420,000 with a yieldof 82%.

EXAMPLE 535-Dimethylamino-1-Naphthalenesulfonyl(Trifluoro-Methanesulfonyl)Imide

[0351] In 20 ml of anhydrous acetonitrile, 5.39 g (20 mmoles) of5-dimethyl-amino-1-naphthalenesulfonyl chloride (commercially availablefrom Aldrich) was reacted with 2.98 g (20 mmoles) oftrifluoromethane-sulfonamide CF₃SO₂NH₂ 4.49 g (40 mmoles) of DABCO.After 24 hours under stirring at room temperature, the reaction mixturewas filtered to remove the DABCO hydrochloride formed, and acetonitrilewas evaporated. The product obtained was recrystallized in 20 ml ofwater containing 2.98 g (40 mmoles) of potassium chloride. Afterfiltration and drying, 5.63 g of potassiumtrifluoromethane-sulfonyl(5-dimethylamino-1-naphthalenesulfonyl)imide(69% yield) was recovered with a purity characterized by a fluorine andproton RMN higher than 99%.

[0352] Microanalysis has given: H 2.96 (2.88); C 37.23 (37.14); N 6.41(6.66); F 13.98 (13.56); S 15.65 (15.25); K 9.46 (9.3).

[0353] This fluorescent salt is soluble in most polar organic solvents(acetonitrile, tetrahydrofurane, DMF, . . . ).

EXAMPLE 54 N-Trifluoromethanesulfonyl-2-Aminoacridine

[0354] Using a process similar to the one described in Example 34, themagnesium salt of N-trifluoromethanesulfonyl-2-aminoacridine wasobtained by action of trifluoromethanesulfonyl chloride on magnesium2-aminoacridine in tetrahydrofurane. After evaporation of the solvents,the product was reclaimed in water and treated with tetraethylammonium(10% in excess) in water, and a precipitate then appeared. Afterfiltration and drying, N-trifluoromethanesulfonyl-2-aminoacridinetetraethylammonium (66% yield) was obtained with a purity determined bya proton and fluorine RMN higher than 99%.

[0355] Microanalysis has given: H 6.11 (6.39); C 59.25 (59.85); N 6.89(6.34); F 12.25 (12.91); S 7.95 (7.26).

[0356] In the same manner, N-fluorosulfonyl-2-aminoacridinetetraethylammonium was obtained from fluorosulfonamide.

[0357] This salt is soluble in most usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide), as well as in polymers with low polarity such as methylpolymethacrylate.

[0358] These salts have a very substantial fluorescence. Adichloroethane solution of polymethylmethacrylate (PMM) and of either ofthese anunonium salts (97:3) was prepared. Fluorescent deposits wereobtained on a number of supports (glass, polymer, . . . ).

EXAMPLE 55 1,3-Phenylsulfonamide-N,N′-Perfluoro-1-Butane-SulfonylRhodamine B

[0359] To 2.9 g of sulforhodamine B (5 mmoles, commercially availablefrom Aldrich) in 50 ml of anhydrous dimethylformamide, there is added941 mg of the potassium salt of trifluoromethanesulfonic acid CF₃SO₃K (5mmoles). After 2 hours under stirring, 1.27 g of oxalyl chlorideClCOCOCl (10 mmoles) in solution in 10 ml of anhydrous dichloromethanewas added slowly. The reaction was continued overnight under argon, and6.74 g of potassium perfluoro-1-butanesulfonamide C₄F₉SO₂NHK (20 mmoles)were added. After 48 hours, dimethylformamide was evaporated and theresidue was recrystallized in 40 ml of water. After filtration anddrying, there is obtained 4.11 g (71% yield) of the potassium salt of1,3-phenyl-sulfonamide-N,N′-(perfluoro-2-butanesulfonyl) rhodamine Bhaving a purity characterized by a proton and fluorine RMN higher than99%.

[0360] Microanalysis has given: H 2.76 (2.52); C 36.56 (36.27); N 4.96(4.83); F 29.99 (29.51); S 11.55 (11.07); K 3.17 (3.37).

[0361] By the same process, the di-potassium salt of1,3-phenylsulfonamide-N,N′-fluorosulfonyl rhodamine B was obtained fromthe potassium salt of fluorosulfonamide, the di-potassium salt of1,3-phenylsulfonamide-N,N′-trifuoromethanesulfonyl rhodamine B wasobtained from the potassium salt of trifluoromethanesulfonamide and thedi-potassium salt of1,3-phenylsulfonamide-N,N′-pentafluoroethane-sulfonyl rhodamine B wasobtained from pentafluorosulfonamide.

[0362] Lithium salts were obtained by metathesis with lithium chloridein tetrahydrofurane.

[0363] These zwitterions have intense dying properties. They are solublein polar polymers and permit the production of colorants containinglasers. The sulfonimide groups also enable them to be adsorbed onoxides, in particular nano-particular titanium dioxide; they then act asa sensitizer towards visible radiation, in particular in applications tophotovoltaic cells.

EXAMPLE 56 Trifluoromethanesulfonyl(Anthracenyl-9-Ethanesulfonyl)Imide

[0364] In a Parr chemical reactor, there is introduced a solution of9.36 g of the potassium salt of trifluoromethanesulfonamide CF₃SO₂NHK(50 mmoles) and of 264 of crown ether, 18-Crown-6 (acting as complexingagent of the potassium cation), in 60 ml of anhydrous acetonitrile.After closing the reactor, the reactor was flushed with argon during 15minutes before isolating it. There is then introduced 6.41 g of sulfurdioxide SO₂ (50 mmoles, commercially available from Fluka) and, after 10minutes, 10.21 g of 9-vinylanthracene (50 mmoles, commercially availablefrom Lancaster) in solution in 20 ml of anhydrous dichloromethane. After6 hours at room temperature, the temperature of the reactor was set at50° C. and kept therein during 48 hours, and the solvent was evaporatedand the product was dried. The potassium salt oftrifluoromethanesulfonyl(anthracenyl-9-ethanesulfonyl)imide wasrecovered in quantitative yields with a purity characterized by afluorine and proton RMN higher than 99%.

[0365] Microanalysis has given: H 2.78(2.88); C 44.53 (44.83); N 3.33(3.07); F 12.01 (12.51); S 14.36 (14.08); K 8.99 (8.58).

[0366] Using the same process, the potassium salt offlurosulfonyl(anthracenyl-9-ethanesulfonyl)imide was obtained.

[0367] This salt is soluble in most usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

EXAMPLE 57N,N′,N″,N′″-Perfluorobutanesulfonyl-Nickel(I)Phtalocyaninetetrasulfonamide

[0368] To 4.9 g of the sodium salt of Nickel(II)phthalocyaninetetrasulfonic acid (5 mmoles, commercially available fromAldrich) in 40 ml of anhydrous dimethylformamide, there is slowly added2.54 g of oxalyl chloride ClCOCOCl (20 mmoles) in solution in 10 ml ofanhydrous dichloromethane. After 4 hours under stirring, the reactionmixture was centrifuged, the liquid floating on the surface was removed,and the decanted product was reclaimed in 40 ml of anhydrousdimethylformamide. Then, 13.5 g of the potassium salt ofperfluoro-1-butanesulfonamide C₄F₉SO₂NHK (40 mmoles) were added. After48 hours, the dimethylformamide was evaporated and the residue wasrecrystallized in 50 ml of water containing 1.49 g (20 mmoles) ofanhydrous potassium chloride. After filtration and drying, there isobtained 9.54 g (81% yield) of the potassium salt ofN,N′,N″,N′″-perfluorobutanesulfonyl-Nickel(II)phtalocyaninetetrasulfonamide having a purity characterized by a protonand fluorine RMN higher than 99%.

[0369] This salt is soluble in most usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers to which it gives an intense bluecolor and which is stable towards light. This salt, as well as analogousnickel, iron or manganese salts are useful as catalysts for thereduction of oxygen.

EXAMPLE 58

[0370] In 30 ml of THF, 6.76 g of pentafluoropyridine (40 mmoles,commercially available from Aldrich) are reacted with 7.49 g (40 mmoles)of the potassium salt trifluoromethanesulfonamide CF₃SO₂NHK in thepresence of 4.49 g (40 mmoles) of DABCO. After 48 hours under stirring,the solvent was evaporated and the residue was recrystallized in 20 mlof water. After filtration and drying, 8.03 g of the potassium salt oftrifuoromethanesulfonyl(4-azapentafluoropyridine)imide (76% yield) wereobtained, having a purity determined by a fluorine RMN higher than 99%.

[0371] According to the same process, the potassium salt oftrifuoromethanesulfonyl((4,6-dinitro-2-trifluoromethyl)phenyl)amide wasobtained from 10.82 g of 2-chloro-3,5-dinitrobenzo-trifluoride (40mmoles, commercially available from Aldrich), having a purity determinedby a fluorine, proton and carbon RMN higher than 99%

[0372] Lithium salts were obtained by ionic exchange with lithiumchloride in THF.

[0373] These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers.

EXAMPLE 59N,N′-Trifluoromethanesulfonyl-3,4-Amino-3-Cyclobutene-1,2-Dione

[0374] In a glove box under argon, 5.61 g (30 mmoles) oftrifluoromethanesulfonamide in solution in 40 ml of anhydroustetrahydrofurane at −30° C., there is added drop-wise 30 ml of a 1 Msolution of dibutylmagnesium (C₄H₉)₂Mg (30 mmoles, commerciallyavailable from Aldrich) in heptane. After 4 hours at −30° C., there isslowly added 2.55 g (15 mmoles) of 3,4-diethoxy-3-cyclobutene-1,2-dione.The reaction was continued during 2 hours at −30° C. and for 24 hours atroom temperature. The solvents were then evaporated, the product wasreclaimed in water and extracted with ether after acidification of theaqueous solution. The compound obtained after evaporation of ether wassublimated under secondary vacuum at 40° C., and after 24 hours 5.02 gof N,N′-trifluoromethanesulfonyl-3,4-amino-3-cyclobutene-1,2-dione (89%yield) were recovered on a cold finger.

[0375] Microanalysis has given: H 0.78 (0.54); C 18.89 (19.16); N 7.04(7.45); F 29.88 (30.3); S 16.71(17.04).

[0376] The lithium salt was obtained by treating the acid with lithiumcarbonate Li₂CO₃ in water.

[0377] These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

[0378] These salts have two reversible redox couples, they arereoxidized to neutral state at the potential of oxidation of LiCoO₂ atthe end of the charge. By dissolution in a liquid, gel or polymerelectrolyte, they provide for a protection during overcharge, thusacting as a redox shuttle. They also make it possible to produceelectrochrome systems with colorants.

EXAMPLE 60 1,1′-(Propylsulfonamide-N-Trifluoromethanesulfonyl) Ferrocene

[0379] During a first step, a ferrocene dilithium complexed withtetramethylethylenediamine (TMEDA) was prepared in the following manner:by operating in a glove box under argon, 37 ml of TMEDA (247 mmoles)freshly distilled and 40 ml of anhydrous hexane were placed in a 1 literflask. Then, 154 ml of a 1.6 M solution of butyllithium in hexane (247mmoles, commercially available from Aldrich) were added drop-wise. After10 minutes, 18.6 g of ferrocene (100 mmoles) in solution in 500 ml ofanhydrous hexane were added drop-wise while maintaining a strongstirring of the solution. After standing overnight, orange crystalsappeared in the solution, which were recovered by filtration of thesolution on a fritted glass of porosity No. 4. After drying undervacuum, there is obtained 28.4 g of 1,1′-dilithio-ferrocene·2 TMEDA (66%yield) which are kept under argon.

[0380] 8.61 g of this compound (20 mmoles) in 30 ml of anhydrousacetonitrile were thereafter treated with 4.89 g of 1,3-propane sultone(40 mmoles) in a glove box. After 24 hours at room temperature, 2 dropsof dimethylformamide were added into the reaction mixture, and 5.08 g ofoxalyl chloride ClCOCOCl (40 mmoles) in solution in 15 ml of anhydrousdichloromethane were added slowly. After 4 hours at room temperature,14.97 g of the potassium salt of trifluoromethanesulfonamide (80 mmoles)were added. The reaction continued for 24 hours, then the solvent wasevaporated. The compound collected was then recrystallized in 30 ml ofwater containing 3 g of potassium chloride. After filtration and drying,10.2 g of a di-potassium salt of1,1′-(propylsulfonamide-N-trifluoromethane-sulfonyl)ferrocene (66%yield) were recovered, in which the purity is characterized by a protonand fluorine RMN higher than 97%.

[0381] Microanalysis has given: H 2.38 (2.62); C 28.72 (28.13); N 3.13(3.64); F 15.16 (14.83); S 17.12 (16.68); K 10.56 (10.17); Fe 7.65(7.27).

[0382] By a similar process, the di-potassium salt of1,1′-(propylsulfonamide-N-fluorosulfonyl)ferrocene was obtained.

[0383] Lithium salts were obtained by treating the acid with lithiumcarbonate Li₂CO₃ in water.

[0384] These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

[0385] These salts have a reversible redox couple. In poly (ethyleneoxide) a reversible potential ≈3.4 V towards a lithium electrode wasdetermined on a platinum electrode having a diameter of 125 μm.

[0386] By dissolution into a liquid, gel or polymer electrolyte, thesalts gave protection during overcharge, thus acting as a redox shuttle.They also enable to produce electrochrome systems with colorants.

EXAMPLE 61 9-10-(Propylsulfonamide-N-Trifluoromethane-Sulfonyl)Phenazine

[0387] By operating in a glove box under argon, there is introduced intoa Nalgene 30 ml flask 1.8 g of phenazine (10 mmoles) and 139 mg ofmetallic lithium. Then, there is added 20 ml of anhydroustetrahydrofurane and agate balls. After closing the flask, it wasrotated upon itself, outside the glove box, on the shaft of a motor.Tetrahydrofurane rapidly turned to a dark purple color, whichcharacterizes mono-lithium phenazine. After 24 hours, there is obtainedin suspension an orange precipitate of 9,10-di-Li-dihydrophenazine. 6.56g of the potassium salt oftrifluoromethanesulfonyl(3-chloropropanesulfonyl)imide (20 mmoles),obtained in Example 8, were then added under argon. The flask was thenagain rotated upon itself during 24 hours, and the reaction mixture wasfiltered under argon to remove the precipitate of potassium chloridewhich is formed during the reaction, and the balls of agate.

[0388] After evaporation of the solvent, 6.52 g of the di-lithium saltof 9-10-(propylsulfonamide-N-trifluoromethanesulfonyl)phenazine wererecovered.

[0389] This salt is soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

[0390] This salt has two reversible redox couples. In poly (ethyleneoxide), on a platinum electrode of a diameter of 125 μm, it was shownthat there is a first redox couple having a potential 3.2 V and a secondredox couple having a potential ≈3.8 V, these potentials being measuredtowards a lithium electrode.

[0391] By dissolution in a liquid, gel or polymer electrolyte, this saltprovides protection in overcharge, thus acting as a redox shuttle.

[0392] This salt may also be used in electrochrome systems withcolorants. It was thus possible to produce an electrochrome glass paneby depositing on a glass plate covered with a conductive layer of ITO(indium and tin oxide), a solution in acetone of this compound andpoly(benzodide-co-oxide of ethylene) having a molecular weight ≈1,100g/mole. After evaporation of the solvent and drying, in a glove box,there is deposited on the layer of copolymer, a second glass electrodecovered with a conductive layer of ITO (indium and tin oxide). Afterhaving sealed the assembly to make it impervious, a potential of 1,250mV was applied on the outside by means of a potentiostat. The system wasthen colored in intense blue. By applying a potential of −500 mV, arelatively rapid discoloration of the system (lower than 60 s) wasnoted.

[0393] Such an electrochrome system is easy to prepare, even for largesize systems (larger than m²) which use either a glass or a polymerwhich is suitably treated as a conductive transparent electrode.Moreover, the energy required to maintain the coloration is relativelylow, i.e. lower than 1 W/m².

EXAMPLE 62 2,2′-Azinobis(3-Ethylbenzothiazoline-6(Sulfonyl(Trifluoromethanesulfonyl)Imide)

[0394] First, the di-sodium salt of2,2′-azinobis(3-ethylbenzo-thiazoline-6-sulfonic) acid was prepared fromits di-ammonium salt (commercially available from Aldrich), by treatingit with a titrated solution of sodium hydroxide. After evaporation anddrying, the di-sodium salt was recovered in quantitative yield. To 1.12g of this compound (2 mmoles) in 10 ml of anhydrous acetonitrile, thereis slowly added 508 mg of oxalyl chloride ClCOCOCl (4 mmoles) insolution in 1 ml of anhydrous dichloromethane. After 4 hours understirring, there is added 2.7 g of the potassium salt ofperfluoro-1-butanesulfonamide C₄F₉SO₂NHK (4 mmoles). After 48 hours, theacetonitrile was evaporated and the residue was recrystallized in 10 mlof water. After filtration and drying, there is obtained 1.81 g of thefollowing compound:

[0395] The di-tetraethylammonium salt was prepared by treating thisproduct with tetraethylammonium chloride in water. Thedi-tetraethylammonium salt was thereafter recovered by extraction withdichloromethane.

[0396] By oxidation, this compound gives a radical and a biradical whichare stable zwitterions. In addition, this compound is useful asoxidation catalyst between an oxygenated aqueous phase and anon-miscible organic phase containing the species to be oxidized.

EXAMPLE 63 Poly(N-2-Trifluoromethanesulfonyl-Aniline)

[0397] To 21.63 g of 1,2-phenylenediamine C₆H₄(NH₂)₂ (200 mmoles), in200 ml of anhydrous dichloromethane at −20° C., there is added drop-wise56.42 g of trifluoromethanesulfonic anhydride (CF₃SO₂)20 (200 mmoles) insolution in 50 ml of anhydrous dichloromethane. After standing overnightat −20° C. and 4 hours at room temperature, the dichloromethane wasevaporated. The residue was then recrystallized in 10 ml of a 4 Msolution of potassium hydroxide KOH. After filtration and drying, 47.87g of the potassium salt ofN-2-trifluoromethanesulfonyl-1,2-phenylenediamine was recovered (86%yield). This compound (172 mmoles) was then stirred in 86 ml of a 2 Msolution of hydrochloric acid. After 24 hours, and after filtration anddrying, 26.85 g (65% yield) of the ammonium salt ofN-2-trifluoromethanesulfonyl-1,2-phenylenediamine C₆H₄(NSO₂CF₃)(NH₃ ⁺)were recovered. 12.01 g of this compound (50 mmoles) were then dissolvedin 200 ml of water, 136 mg of silver nitrate (800 μmoles) were added,and the solution was brought to 0° C. A solution of 11.4 g of ammoniumpersulfate (NH₄)₂S₂O₈ (50 mmoles) in 100 ml of water was also preparedand this solution was brought to a temperature of 0° C. Then thepersulfate solution was added under stirring for a few minutes to asolution of the aniline salt. After about 10 minutes, the solutionstarted to assume a color. After 3 hours at a temperature lower than 5°C., the solution was concentrated to a volume 100 ml and 3.73 g ofpotassium chloride were added. The precipitate present in the solutionwas then recovered by filtration. After drying, 5.9 g of the followingblack powder was obtained:

[0398] This electronically conductive polymer has an electronicconductivity determined by the method of four peaks of 8.7 S.cm⁻¹. Thisconductivity is stable even when the material is exposed to air.

EXAMPLE 641-Dodecyl-1,1,1,3,3,3-Hexafluoro-2-Propanoxysulfonyl(Trifluoro-Methanesulfonyl)Imide

[0399] To 18.11 g (100 mmoles) of 6-bromo-1-hexanol and 11.22 g (100mmoles) of DABCO in 100 ml of anhydrous THF at −20° C. there is slowlyadded 19.06 g (100 mmoles) of tosyl chloride. After 24 hours understirring at −20° C., the reaction mixture was filtered to remove theprecipitate of DABCO hydrochloride. After evaporation of the solvent,6-bromo-1-hexanol tosylate CH₃ΦSO₂O(CH₂)₆Br was recoveredquantitatively. This compound was thereafter dissolved in 200 ml of THFwith 40 g of aniline ΦNH₂ and this solution was brought to refluxovernight. After cooling, 300 ml of water were added and the organicphase was extracted with ether. After washing with water, the etherphase was dried with magnesium sulfate. There is obtained, afterevaporation and drying, 23 g of N-(6-bromohexyl)aniline.

[0400] By operating in a glove box under argon, 18.96 g (50 mmoles) oftrifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide,prepared as in Example 37, were put in solution in 10 ml of anhydroustetrahydrofurane. After having brought this solution to −20° C., 50 mlof a 1 M solution in tetrahydrofurane of potassium tert-butoxide(CH₃)₃COK (50 mmoles, commercially available from Aldrich) were slowlyadded. After 15 minutes, 12.81 g (50 mmoles) of N-(6-bromohexyl)anilinewere added. The reaction was continued during 2 hours at −20° C., thenfor 24 hours at room temperature. After 48 hours under stirring, thesolvent was evaporated and the residue was recrystallized in 30 ml ofwater. After filtration and drying, the potassium salt of1-(6-anilino-1-hexyl)-1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl(trifluoromethane-sulfonyl)imidewas obtained, which has a purity characterized by a proton, carbon andfluorine RMN higher than 97%. 12.13 g of this compound (20 mmoles) werethereafter dissolved in 20 ml of water, 68 mg of silver nitrate (400μmoles) were added, and the temperature of the solution was brought to0° C. Also, a solution of 4.56 g of ammonium persulfate (NH₄)₂S₂O₈ (20mmoles) in 100 ml of water was prepared and this solution was brought to0° C. Then, the solution of persulfate was added during a few minutes tothe solution of the salt of aniline under stirring. After about 10minutes, the solution started to turn to a bluish green color. After 3hours at a temperature lower than 5° C., the solution was concentratedto a volume ≈60 ml, and 1.49 g of potassium chloride were added. Theprecipitate present in the solution was then recovered by filtration.After drying, there is obtained 3.9 g of a black powder of the followingcompound:

[0401] This polymeric compound which comprises a doping anion verydelocalized in its structure, has the properties of an electronicconductor (PCE). The low basic character of this anion improves thestability of the polymer, in particular in humid medium. Theconductivity determined by a four peaks measurement, before exposing thePCE to a humid atmosphere, was of the order of 4 S.cm⁻¹.

[0402] This material was tested as a cathode for a battery. The batteryhad the following structure:

[0403] a composite cathode consisting of 40% by volume of the copolymerobtained in the present example and 60% by volume of poly (ethyleneoxide) of molecular weight 3×10⁵;

[0404] an electrolyte consisting of a poly (ethylene oxide) film ofmolecular weight 5×10⁶ the lithium salt oftrifluoromethanesulfonyl-(butanesulfonyl)imide, obtained in Example 39,at a concentration O/Li=20/1;

[0405] a metallic lithium anode.

[0406] After mounting the assembly in a button shaped battery casing,the battery obtained was cycled at a temperature of 60° C. between 3 Vand 3.9 V. More than 1,000 cycles of charge/discharge were carried outwhile preserving 80% of the capacity of the first cycle.

[0407] In addition, the polymeric compound of the present example is agood corrosion inhibitor of ferrous metals in acid or chloride media.The treatment of surfaces to be protected is simply carried out bydepositing a solution of PCE in a mixture of water anddimethylformamide, in the form of a paint, followed by drying andthermal treatment at 100° C. This polymeric compound gives adherentconductive deposits whose conductivity is stable in air on plasticstreated by Corona effect.

EXAMPLE 65Poly(2-[2-(3-Thienyl)Ethoxy]Ethanesulfonyl(Trifluoro-Methanesulfonyl)Imide)

[0408] By a process similar to the one used for the synthesis of7,8-octene-3,6-oxa-1-sulfonyl-(trifluoromethanesulfonyl)imide (Example15), the potassium salt of2-[2-3(3-thienyl)ethoxy]-ethane-sulfonyl(trifluoromethanesulfonyl)imidewas synthesized from 2-(3-thienyl)ethanol. The product obtained has apurity determined by a carbon and proton RMN higher than 98%.

[0409] 10 ml of a 5×10⁻² M solution of the salt in acetonitrile wasprepared and electropolymerization was carried out in the anodecompartment of an electrochemical cell on an electrode of platinum.There is obtained a conductive flexible film of:

[0410] in which the doping (oxidation) is ensured by cation and electronexchange with the exterior. The conductivity of this material is of theorder of 10 S.cm⁻¹ and it is stable at ambient atmosphere and in humidmedium. An electropolymerization carried out in the presence ofnon-substituted pyrrol or having oxyethylene chains in N or 3 positiongives copolymers which are also stable in which the change of color maybe used for preparing electrochrome system.

EXAMPLE 66 Doped Polyaniline

[0411] In 100 ml of water there is suspended 2.54 g of polyanilinechloride (AC&T, St Égrève, France):

[0412] To 9.81 g of the potassium salt oftrifluoromethanesulfonyl(di-2-ethylhexylaminosulfonyl)imide obtained inExample 28 were then added:

[0413] After 48 hours under stirring, the polyaniline doped withtrifluoromethanesulfonyl)di-2-ethylhexylaminosulfonyl)imide wasrecovered. In this form, it is soluble in toluene. A toluene solution ofthe doped polyaniline was used to produce a film which is anelectronically conductive polymer in which the conductivity, measured bythe method the four peaks, is 6 S/cm, with a good stability in humidmedium.

[0414] From this solution, there is also prepared a film on a support ofpolypropylene (PP) treated by Corona effect. After drying under vacuumat 60° C. during 48 hours, there is obtained a deposit of polyanilinewhich is conductive and adherent and has a thickness lower than 1micron. This type of treatment on plastic materials is particularlyinteresting to produce flexible electrical contactors or systems ofelectromagnetic protections.

EXAMPLE 67 Poly(4-Styrenesulfonyl (Trifluroro Methane Sulfonyl) Imide)

[0415] 20.62 g of poly(sodium-4-styrenesulfonate) having an averagemolecular weight of 10⁶ g/mole (100 mmoles of-SO₃Na), (commerciallyavailable from Aldrich) in suspension in 100 ml of anhydrousdimethylformamide were treated with 14.08 g (110 mmoles) of(chloromethylene)dimethylammonium chloride (commercially available fromAldrich) at room temperature. After 72 hours, the solution becameviscous, and the poly(4-styrenesulfonyl chloride) goes into solution indimethylformamide. To the reaction mixture there is then added 16.4 g(110 mmoles) of trifluoromethanesulfonamide and 24.68 g (220 mmoles) of1 (DABCO). After 24 hours, the solvent was evaporated, the productobtained was reclaimed in 50 ml of water, and treated with 8.2 g ofanhydrous potassium chloride. After 24 hours, the reaction mixture wasfiltered and the product thus recovered was recrystallized in 50 ml ofwater. After drying, there is obtained 26.1 g of the potassium salt ofpoly(4-styrenesulfonyl(trifluoromethanesulfonyl)-imide) (74% yield)having a purity characterized by a proton and fluorine RMN higher than99%.

[0416] The corresponding lithium salt was prepared quantitatively byionic exchange (metathesis) between the potassium salt and lithiumchloride in anhydrous tetrahydrofurane.

[0417] This polyelectrolyte is soluble in most of the usual organicsolvents (tetrahydrofurane, acetonitrile, dimethylformamide, ethylacetate, glymes) and in polar polymers.

[0418] By utilizing an appropriate cation, this polyelectrolyte mayconstitute a doping agent of conjugated electronically conductivepolymers such as polypyrrol or polyaniline.

EXAMPLE 68 Catalysis of an Aldol Condensation

[0419] Diethylaminosulfonyl(trifluoromethanesulfonyl)imide was preparedfrom its potassium salt, obtained in Example 28, according to a processsimilar to the one used in Example 29 to givedimethylaminosulfonyl(trifluoromethanesulfonyl)imide. Following this,2.84 g of this acid (10 mmoles) were treated with 657 mg of ytterbiumoxide Yb₂O₃ (1.67 mmoles) in 20 ml of water. After 24 hours of stirring,the solution was lyophilized, and the product obtained was dried undervacuum during 48 hours at 60° C. The ytterbium salt ofdiethylaminosulfonyl(trifluoromethanesulfonyl)imide (Yb(DETFSI)₃) wasobtained in quantitative yield.

[0420] This salt was used as a catalyst for an aldol condensation in thefollowing manner:

[0421] To 410 mg of Yb(DETFSI)₃ (0.4 mmoles, 10% molar) indichloromethane there is added a mixture of 1.05 g (6 mmoles) of1-ene-3-methyl-1-silylacetal-1-methoxypropene (CH₃)₂C═C(OSiMe₃)OMe and420 mg (4 mmoles) of benzaldehyde in 10 ml of dichloromethane. After 16hours under stirring at room temperature, water was added and theproduct was extracted with dichloromethane. The organic phase was washedwith three fractions of 100 ml of water, and dichloromethane wasevaporated. The residue was then treated with a mixturetetrahydrofurane/HCl 1 M (20:1) during 0.5 hours at 0° C. After dilutingwith hexane, a saturated solution of sodium bicarbonate was added, andthe product was extracted with dichloromethane. The organic phase waswashed with a saturated solution of sodium chloride, and dried withsodium sulfate. After evaporation of the solvents, the raw product waschromatographed on a silica gel.Methyl-3-hydroxy-2,2-dimethyl-phenylpropionate was obtained with a yieldof 89%.

[0422] The same reaction was carried out with a quantity of catalystswhich is decreased by a factor near 10, without decreasing the yield ofthe compound methyl-3-hydroxy-2,2-dimethyl-phenylpropionate. This resultis due to the good solubility in dichloromethane of the ytterbium saltof diethyl-aminosulfonyl(trifluoromethanesulfonyl)imide.

EXAMPLE 69 Catalysis of a Michael Addition

[0423] The ytterbium salt ofdiethylaminosulfonyl-(trifluoromethanesulfonyl)imide, obtained inExample 40, was used as a catalyst in a Michael addition in thefollowing manner: To 410 mg of Yb(DETFSI)₃ (0.4 mmoles, 10% molar),obtained in Example 65 in 15 ml of dichloromethane, there is added amixture of 1.05 g of 1-ene-2-methyl-1-silylacetal-1-methoxypropane(CH₃)₂C═C(OSiMe₃)OMe (6 mmoles) and 840 mg of chalcone (4 mmoles) in 10ml of dichloromethane. After 12 hours under stirring at roomtemperature, water is added and the product was extracted withdichloromethane. The organic phase was washed with three fractions of100 ml of water, and dichloromethane was evaporated. The residue wasthen treated with a mixture of tetrahydrofulrane/HCl 1 M (20:1) during0.5 hours at 0° C. After diluting with hexane, there is added asaturated solution of sodium bicarbonate, the product was extracted withdichloromethane. The organic phase was washed with a saturated solutionof sodium chloride, and dried with sodium sulfate. After evaporation ofthe solvents, the raw product was chromatographed on a silica gel. Thecompound 1,5-dicarbonyl was obtained with a yield of 87%.

[0424] The same reaction was carried out with a quantity of catalystwhich is decreased by a factor close to 10, without decreasing the yieldof the 1,5-dicarbonyl compound. This result is due to the goodsolubility in dichloromethane of the ytterbium salt ofdiethylaminosulfonyl(trifluoromethanesulfonyl)imide.

EXAMPLE 70 Catalysis of a Friedel-Crafts Acylation Reaction

[0425] To 10 ml of a 1 M solution of triethylaluminum (C₂H₅)₃Al (10mmoles) (commercially available from Aldrich in toluene, there is slowlyadded under argon 2.84 g oftrifluoromethanesulfonyl(diethylaminosulfonyl)imide (C₂H₅)₂NSO₂NHSO₂CF₃(10 mmoles) in solution in 10 ml of toluene, hereinafter designatedHDETFSI, previously prepared from the corresponding potassium salt byextraction with ether. After 2 hours under stirring, the solvent wasevaporated and the corresponding aluminum salt was dried and stored in aglove box.

[0426] This compound was used as catalyst for a Friedel-Crafts acylationreaction in the following manner; in 40 ml of anhydrous nitromethane,there is added 616 mg of Al(DETFSI)₃ (700 μmoles), and 1.08 g of anisol(10 mmoles) and 2.04 g of acetic anhydride. After stirring for 5 minutesat 21° C., the reaction mixture was diluted with 50 ml of ether and thereaction was inhibited with 100 ml of a saturated solution of sodiumbicarbonate NaHCO₃. After filtration on Celite, the solution wasextracted with three fractions of 50 ml of ether, and the ether phasewhich was collected was washed with a saturated solution of potassiumchloride. After drying the ether phase with magnesium sulfate andevaporation, 1.46 g of p-methoxyacetophenone (97% yield) were recoveredwith a purity characterized by a proton RNN higher than 99%.

EXAMPLE 71 Catalysis of a Diels & Alder Reaction

[0427] Various salts according to the invention were used as catalystsof a Diels Alder reaction, namely the reaction of methylvinylketone withcyclopentadiene.

[0428] The salts used are the lanthanum salt oftrifluoromethanesulfonyl(R(−)-1-phenyl-2,2,-trifluoroethanoxysulfonyl)imide(LaPTETFSI) prepared according to Example 46, the lanthanum salt of(1R)-(−)-10-camphor-sulfonyl)perfluorobutanesulfonyl)imide (LaCSTFSI)prepared according to Example 48, the lanthanum salt of(1R)-(−)-trifluoromethanesulfonyl(N-methoxybutyl-N-2-butyl-3—methyl)aminosulfonyl)imide(LaMBBMTFSI) prepared according to Example 47 and the scandium salt oftrifluoromethanesulfonyl(N-(1S)-(+)-ketopinic-acetyl-N-methylsulfonyl)imide (ScKANTFSI) preparedaccording to Example 49.

[0429] For each of the above salt, the following process was used.

[0430] To a solution of 651 mg of freshly distilled cyclopentadiene (10mmoles) and 701 mg of methylvinylketone in 10 ml of dichloromethane,there are added 200 μmoles of the lanthanum or scandium salt of chiral.After 24 hours at room temperature, the reaction mixture was filtered toremove the catalyst in suspension. In all cases, there is obtained ayield, determined by chromatography in gaseous phase, higher than 90%.After separating the different reaction products on a chiral column, theenantiomeric excesses were determined by RMN. These salts enable toobtain a chiral catalysis which is made obvious by the enantiomericexcesses given in the following table. Chiral Catalyst EnantiomericExcesses LaPTETESI 69% LaCSTFSI 76% LaMBBMTFSI 72% ScKANTFSI 67%

EXAMPLE 72 Acrylonitrile/4Styrenesulfonyl(Trifluoromethanesulfonyl)Imide Copolymer

[0431] A solution of 19.27 g of the lithium salt of4-styrenesulfonyl(trifluoromethanesulfonyl)imide (60 mmoles), 2.12 g (40mmoles) of acrylonitrile and 100 mg of1,1′-azobis)cyclohexanecarbonitrile) (1 mmoles) in 100 ml of anhydroustetrahydrofurane was degassed by flushing with dry argon. Then, underargon, copolymerization of acrylonitrile with the styrene derivative wascarried out by heating the reaction mixture at 60° C. during 48 hours.After cooling, the solution was concentrated, and the polymer wasrecovered by reprecipitation in ether. After filtration and drying,17.54 g of the lithium salt ofpoly(acrylonitrile-co-4-styrenesulfonyl-(trifuoromethanesulfonyl)imide(PANSDTFSI) were recovered with a yield of 82%.

[0432] This polymer may be used for preparing gelled polymerelectrolytes with fixed anions, the polymer ensuring a double matrixfunctionality enabling to obtain the polyelectrolyte gel.

[0433] A gel electrolyte consisting of 30 weight percent ofpolyelectrolyte, 35% of ethylene carbonate and 35% of propylenecarbonate was prepared. This gel has good mechanical properties and aconductivity of 9.6×10⁻⁴ S.cm⁻¹ at 30° C. The number of cationictransport in this electrolyte is 0.85. An electrochemical generator wasprepared comprising an anode consisting of coke carbon (80% in volume)mixed with the copolymer (PANSDTFSI) as binder (20% by volume), theabove gelled electrolyte, and a composite cathode consisting of carbonblack (6% by volume), LiNiO₂ (75% by volume) and the copolymer(PANSDTFSI) (20% by volume). This generator has good performances incycling at 25° C. (1,000 cycles of charge/discharge between 3 and 4.2 Vby maintaining a capacity higher than 80% of the capacity during thefirst cycle). Also, it has very good performances during calls for powerdue to the fact of the utilization of fixed anions. The utilization offixed anions has also enabled to improve the evolution of the resistanceof the interface.

EXAMPLE 73 Acrylonitrile/4-Styrenesulfonyl(Trifluoromethanesulfonyl)Imide Copolymer

[0434] According to a process similar to the one used in Example 72, acopolymer of acrylonitrile (3% molar) and of the lithium salt of4-styrenesulfonyl(trifluoromethanesulfonyl)-imide (97% molar) wassynthesized.

[0435] This copolymer has antistatic properties, contrary topolyacrylonitrile (PAN) which, in the form of alkaline or ammonium salt,is widely used in the form of textile fibre. Moreover, spinning of thiscopolymer is easier than with non-modified PAN.

[0436] The copolymer has very good interaction with cationic coloringmatters such as methylene blue, which makes it a material of interestfor colored textile fibres, the stability of the color being clearlyimproved with respect to the known copolymer of acrylonitrile andmethallylsulfonate.

EXAMPLE 74 VinylideneFluoride/2,2-Fluorovinylsulfonyl-(Trifluoromethanesulfonyl)ImideCopolymer

[0437] In a chemical reactor, there is introduced a solution of 8.43 g(30 mmoles) of 2,2-fluorovinylsulfonyl(trifluoromethanesulfonyl)imideobtained in Example 24 and 100 mg of1,1′-azobis(cyclohexane-carbonitrile) in 100 ml of anhydroustetrahydrofurane. After flushing the reactor under argon, there isintroduced with a sieve, 4.48 g of vinylidene fluoride CF₂CH₂ (70mmoles, commercially available from Air Liquide). Copolymerization wasthen carried out under argon by heating the reaction mixture at 60° C.during 48 hours. After cooling, the solution was concentrated, and thepolymer was recovered by reprecipitation in ether. After filtration anddrying, 10.2 g of the lithium salt ofpoly(vinylidenefluoride-co-2,2-ethanesulfonyl(trifluoromethane-sulfonyl)imide(PFVESTFSI) were recovered with a yield of 79%.

[0438] This polymer enables production of gelled polymer electrolyteswith fixed anions, the polymer ensuring a double functionality of matrixenabling to obtain the gel of polyelectrolytes.

[0439] There is prepared a battery of the same type as the one describedin Example 72 and analogous performances were obtained.

EXAMPLE 75 AGE/Epoxy-Half TFSI/OE Copolymer

[0440] In a chemical reactor, there is introduced a solution of 15.37 g(50 mmoles) of the potassium salt of3,4-epoxybutane-1-sulfonyl(trifluoromethanesulfonyl)imide, prepared asin Example 13, and 685 mg (6 mmoles) of allylglycidylether in 100 ml ofanhydrous tetrahydrofurane. After flushing the reactor with argon, thereare introduced with a sieve 6.34 g (146 mmoles) of 1,2-epoxide in 100 μlof a 10⁻² M solution of potassium t-butoxide in THF. Polymerization wasthen carried out under argon by heating the reaction mixture at 60° C.during 48 hours. After cooling, the solution was concentrated, and thepolymer was recovered by reprecipitation in ether. After filtration anddrying, 15.9 g (71% yield) of the potassium salt ofpoly(oxyethylene-co-3,4-epoxybutanesulfonyl-(trifluoromethanesulfonyl)imide-co-allylglycidyl-ether)were recovered.

[0441] This polymer enables to prepare gelled polymer electrolytes withfixed anions, the polymer ensuring a double matrix functionalityenabling to obtain the gel of polyelectrolytes. It may be crosslinkedduring the process of preparing an electrochemical system containingsame.

[0442] With this polyelectrolyte, a battery similar to the one describedin Example 22 was prepared, which has given similar performances.

EXAMPLE 76 Polysiloxane With Fixed Anions

[0443] In a three-neck flask provided with a cooler, a mechanicalstirrer and a neutral gas inlet (Argon), 9.5 g of a copolymer ofdimethylsiloxane and (hydrogeno) (methyl)-siloxane (HMS 301 25% SiH,M_(w) 1900 Gelest Inc., Tullytown, Pa., USA) were placed in solution intetrahydrofurane; 9.13 g of the lithium salt ofvinylsulfonyl(trifluoromethanesulfonyl)imide and 70 mg of chloroplatinicacid H₂PtCl₆. were then added. The mixture was heated to reflux during 4hours. The polymer was then reprecipitated in ethanol.

[0444] A copolymer of dimethylsiloxane and of the lithium salt of(N-trifluoromethanesulfonyl-ethylsulfonamide) (methyl)-siloxane was thusobtained.

[0445] This polymer is soluble in most of the organic solvents,including in amounts >2% in oils or silicon materials, thus giving themantistatic properties.

EXAMPLE 77 Li/POENV20s Battery

[0446] The lithium salt ofdimethylaminosulfonyl-(trifluoromethanesulfonyl)imide, preparedaccording to Example 25, was tested in an electrochemical generatoraccording to the lithium-polymer technology. The generator was preparedby superposing the following layers:

[0447] a stainless steel current collector having a thickness of 2 mm;

[0448] a cathode consisting of a button shaped film of compositematerial having a thickness of 89 μm and consisting of vanadium dioxide(45% by volume), Shawinigan black (5% by volume) and a polyethyleneoxide of molecular weight Mw=3.105 (50% by volume);

[0449] an electrolyte consisting of a button shaped film of polyethyleneoxide of molecular weight Mw=5.106 containing the lithium salt ofdimethylamino-sulfonyl(trifluoromethanesulfonyl)imide at a concentrationO/Li=15/1;

[0450] an anode consisting of a sheet of metallic lithium having athickness of 50 μm;

[0451] a current collector similar to the above mentioned collector.

[0452] The button shaped members constituting the electrodes and theelectrolyte were cut in a glove box and piled in the order indicatedabove. The collectors were then placed on both sides of the pileobtained.

[0453] The assembly was sealed in a button shaped battery casing, whichsimultaneously enables to protect the generator from the atmosphere andto exercise a mechanical stress on the films. The battery was thenplaced in an enclosure under argon mounted in a dryer at a temperatureof 60° C. It was then cycled between 1.8 and 3.3 V at a rate of chargeand discharge of C/10 (charged or discharged nominal capacity in 10hours).

[0454] The cycling curve is given in FIG. 1. In this figure, the use, U,expressed in % is given in ordinate, and the number of cycles C is givenin abscissae.

EXAMPLE 78 Extrusion

[0455] In a Warner & Pfilder extruder, there is introduced under anargon atmosphere, poly (ethylene oxide) of a molecular weight M_(w)=10⁵in the form of button shaped members 2 mm in diameter and a mixture ofthe lithium salt of dodecylsulfonyl(trifluoromethanesulfonyl)imideprepared according to a process analogous to the one of Example 39, thepotassium salt of Igepal®CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide prepared by aprocess analogous to the one of Example 43, vanadium oxide V₂O₅ crushedto a particle size smaller than 5 μm, and carbon black. The mixture ofcomponents was then introduced in such proportions that vanadium oxiderepresents 40% of the total volume, Shawinigan black 5%, the potassiumsalt of Igepal® CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide 2%,and the mixture poly (ethylene oxide)/lithium salt ofdedecylsulfonyl(trifluoromethanesulfonyl)imide 53%, the lithium saltbeing at a concentration O/Li=15/1. The mixture was then extruded at atemperature of 100° C. in the form of a band 14 cm wide and a thicknessof 63 μm.

[0456] This film which can be used as cathode, was directly placed on asheet of stainless steel 8 μm thick.

[0457] This film of composite cathode was itself covered with a film ofelectrolyte 30 μm thick obtained by extrusion of a mixture of poly(ethylene oxide) of molecular weight M_(w)=3.10⁵ and a lithium salt ofdodecylsulfonyl(trifluoromethanesulfonyl)imide at a concentrationO/Li=45/1.

[0458] The mixture was then laminated with a film of lithium 20 μmthick. There is thus obtained an electrochemical generator according tothe lithium-polymer technology.

[0459] The cycling curve of this generator at a rate of charge anddischarge of C/10 is represented in FIG. 2. In this figure, the use, U,expressed in % is given in ordinate, and the number of cycles C is givenis abscissae.

[0460] The salts of the present invention contain long alkyl chains suchas the potassium salt of Igepal®CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide or the lithium saltof dedecyl-sulfonyl(trifluoromethanesulfonyl)imide, enabling toplasticize poly (ethylene oxide). They also facilitate the extrusion offilms of cathodes or electrolytes used during the manufacture ofbatteries according to the technology of lithium-polymer in thin film.Their electrochemical stability also enables to obtain good performancesduring the cycling of these batteries.

1. Ionic compound consisting of an amide or salts thereof, comprising an anionic part associated with at least one cationic part M^(+m) in sufficient number to ensure an electronic neutrality thereto, characterized in that M is a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metallic cation having a valency m, an organic cation having a valency m or an organo-metallic cation having a valency m and in that the anionic part corresponds to the formula R_(F)—SO_(x)—N⁻—Z in which: the group —S(O)_(x)— represents a sulfonic group —SO₂— or a sulfinyl group —SO—; R_(F) is a halogen or a perhalogenated allkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical corresponding to one of the formulae R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— in which R_(A)— represents a non-perhalogenated organic radical; Z represents an electro-attractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from: j) —CN, —NO₂, —SCN, —N₃, —CF₃, R′_(F)CH₂— (R′_(F) being a perfluorinated radical), fluoroaltkyloxy, fluoroalkylthioxy radical, jj) radicals comprising one or more aromatic nuclei possibly containing at least one hydrogen, oxygen, sulfur or phosphorus atom, said nuclei possibly being condensed nuclei and/or said nuclei possibly carrying at least one substituent selected from halogens, —CN, —NO₂, —SCN, —N₃, —CF₃, CF₃CH₂—, CF₂═CF—O—, CF₂═CF—S—, perfluoroalkyl groups, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophoric group and/or at least one anionic ionophoric group; with the proviso that a substituent Z may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_(F)—S(O)_(x)—N—, or a polymer segment; or Z is a radical R_(D)—Y— in which Y is a sulfonyl, sulfinyl or phosphonyl group and R_(D) is a radical selected from the group consisting of: a) alkyl or alkenyl radicals, aryl, arylalkyl, allylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals; b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate group; c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms such as nitrogen, oxygen, sulfur; d) radicals comprising condensed aromatic cycles which possibly comprise at least one heteroatom selected from nitrogen, oxygen, sulfur; e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or alkenylaryl radicals in which the number of carbon atoms carrying at least one halogen is at least equal to the number of non-halogenated carbon atoms, the carbon in α position of group Y not being halogenated when Y is —SO₂—, said radicals possibly comprising functional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanate or thioisocyanate groups; f) radicals R_(C)C(R′)(R″)—O— in which R_(C) is an alkyl perfluorinated radical and R′ and R″ are independently from one another, an hydrogen atom or a radical as defined in a), b), c) or d) above; g) radicals (R_(B))₂N—, in which the R_(B), identical or different, are such as defined in a), b), c), d) and e) above, one of the R_(B) may be a hydrogen atom, or the two radicals R_(B) together form a bivalent radical which forms a cycle with N; h) radicals consisting of a polymer chain; i) radicals having one or more cationic ionophoric groups and/or one or more anionic ionophoric groups; with the proviso that a substituent R_(D) may be a monovalent radical, part of a multivalent radical carrying a plurality of groups R_(F)S(O)_(x)—N—Y—, or a segment of a polymer; with the proviso that, when Y is a sulfonyl or a carbonyl, and R_(D) is a radical such as defined in a), R_(F) is R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)—, CF₃C(R_(A))F— or a perhaloalkyl radical having 1 to 2 carbon atoms.
 2. Compound according to claim 1, characterized in that the organic cation is an onium selected from the group consisting of R₃O⁺ (oxonium), NR₄ ⁺ (ammonium), RC(NHR₂)₂ ⁺ (amidinium), C(NHR₂)₃ ⁺ (guanidinium), C₅R₆N⁺ (pyridinium), C₃R₅N₂ ⁺ (imidazolium), C₂R₄N₃ ⁺ (triazolium), C₃R₇N₂ ⁺ (imidazolinium), SR₃ ⁺ (sulfonium), PR₄ ⁺ (phosphonium), IR₂ ⁺ (iodonium), (C₆R₅)₃C⁺ (carbonium), the radicals R independently representing H or a radical selected from the group consisting of: alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals; cyclic or heterocyclic radicals possibly comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur; cyclic or heterocyclic radicals possibly comprising heteroatoms in the aromatic nuclei; groups comprising a plurality of aromatic or heterocyclic, condensed or non-condensed nuclei, possibly containing at least one nitrogen, oxygen, sulfur or phosphorus atom; with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles possibly enclosing the center carrying the cationic charge.
 3. Compound according to claim 2, characterized in that cation onium is part of the radical Z or of the radical R_(D).
 4. Compound according to claim 2, characterized in that the onium cation is part of a recurring unit of a polymer.
 5. Compound according to claim 2, characterized in that M⁺ is a cationic heterocycle with aromatic character, including at least one alkylated nitrogen atom in the cycle.
 6. Compound according to claim 5, characterized in that the cation is an imidazolium, a triazolium, a pyridinium, a 4-dimethyl-amino-pyridinium, said cations possibly carrying a substitutent on the carbon atoms of the cycle.
 7. Compound according to claim 2, characterized in that the cation M is a group having a bond —N═N—, —N═N⁺, a sulfonium group, an iodonium group, or a substituted or on-substituted arene-ferrocenium cation, possibly incorporated in a polymer network.
 8. Compound according to claim 2, characterized in that the cation is a diaryliodonium cation, a dialkylaryliodonium cation, a triarylsulfonium cation, a trialkylaryl sulfonium cation, or a substituted or non-substituted phenacyl-dialkyl sulfonium cation.
 9. Compound according to claim 8, characterized in that the cation is part of a polymer chain.
 10. Compound according to claim 2, characterized in that M is an organic cation, incorporating a group 2,2′[azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or 2,2′-azobis(2-amidiniopropane)²⁺.
 11. Compound according to claim 1, characterized in that the cation M is a metallic cation selected from the group consisting of cations of alkali metal, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals, cations of rare earth metal and organometallic cations.
 12. Compound according to claim 1, characterized in that the cation is a metallocenium, selected from the group consisting of cations derived from ferrocene, titanocene, zirconocene, indenocenium cations, arene metallocenium cations, cations of transition metals complexed with ligands of phosphine type possibly having a chirality and organometallic cations having one or more alkyl or aryl groups covalently fixed to an atom or a group of atoms, said cations possibly being part of a polymer chain.
 13. Compound according to claim 1, characterized in that R_(F) is a fluorine atom or a perhalogenated alkyl radical having 1 to 12 carbon atoms, or a perhalogenated alkylaryl radical having 6 to 9 carbon atoms.
 14. Compound according to claim 1, characterized in that R_(F) is selected from the radicals R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— in which R_(A) represents an alkyl group, an aryl group, an alkylaryl or arylalkyl group, or a group comprising at least one ethylenic unsaturation and/or a condensable group and/or a dissociable group, a mesomorphous group; a chromophorous group; a self-doped electronically conductive polymer; a hydrolyzable alkoxysilane; a polymeric chain bearing grafts including a carbonyl group, a sulfonyl group, a thionyl group or a phosphonyl group; a group comprising a free radical trap; a dissociating dipole; a redox couple; a ligand complexing agent; a zwitterion; an amino acid or a optically or biologically active polypeptide; a chiral group.
 15. Compound according to claim 1, characterized in that Z is a R_(D)—SO₂— group.
 16. Compound according to claim 1, characterized in that R_(D) is selected from alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicals having 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl or alkenylaryl radicals having 5 to 24 carbon atoms.
 17. Compound according to claim 1, characterized in that R_(D) is selected from alkyl or alkenyl radicals having 1 to 12 carbon atoms and possibly comprising at least one heteroatom O, N or S in the main chain or in a lateral chain, and/or possibly carrying a hydroxy group, a carbonyl group, an amine group, a carboxyl group.
 18. Compound according to claim 1, characterized in that R_(D) is part of a poly(oxyalkylene) radical or a polystyrene radical.
 19. Compound according to claim 1, characterized in that R_(D) is a radical having an iodonium, a sulfonium, oxonium, ammonium amidinium, triazolium, guanidinium, pyridinium, imidazolium, phosphonium or carbonium group, said ionic group totally or partially acting as the cation M⁺.
 20. Compound according to claim 1, characterized in that R_(D) has one or more anionic ionophoric groups consisting of a carboxylate function (—CO₂ ⁻), a sulfonate function (—SO₃ ⁻), a sulfonimide function (—SO₂NSO₂—) or a sulfonamide function (—SO₂N—).
 21. Compound according to claim 1, characterized in that R_(D) includes at least one ethylenic unsaturation and/or a condensable group and/or a group which is dissociable by thermal means, by photochemical means, or by ionic dissociation.
 22. Compound according to claim 1, characterized in that R_(D) represents a mesomorphous group or a chromophorous group or a self-doped electronically conductive polymer or a hydrolyzable alkoxysilane.
 23. Compound according to claim 1, characterized in that Z represents a recurring unit of a polymer chain.
 24. Compound according to claim 1, characterized in that R_(D) includes a group capable of trapping free radicals.
 25. Compound according to claim 1, characterized in that R_(D) includes a dissociating dipole.
 26. Compound according to claim 1, characterized in that R_(D) includes a redox couple.
 27. Compound according to claim 1, characterized in that R_(D) includes a complexing ligand.
 28. Compound according to claim 1, characterized in that R_(D)—Y— is optically active.
 29. Compound according to claim 1, characterized in that R_(D)—Y— represents an amino acid, or an optically or biologically active polypeptide.
 30. Compound according to claim 1, characterized in that R_(D) represents a radical having a valency v higher than 2, including at each of its free end a group R_(F)—S(O)_(x)—N—.
 31. Compound according to claim 1, characterized in that the substituent Z is selected from the group consisting of —OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and —SC₂F₄H, —OCF═CF₂, —SCF═CF₂ and C_(n)F_(2n+1)CH₂— n being a whole number from 1 to
 8. 32. Compound according to claim 1, characterized in that Z comprises a heterocycle, derived from pyridine, pyrazine, pyrimidine, oxadiazole or thiadiazole, which is fluorinated or non-fluorinated.
 33. Ionically conductive material comprising an ionic compound in solution in a solvent, characterized in that the ionic compound is a compound according to claim
 1. 34. Ionically conductive material according to claim 33, characterized in that at least one of the substituents R_(F) or R_(D) of the ionic compound comprises an alkyl group, an aryl group, a alkylaryl group or an arylalkyl group; a mesomorphous group or a group comprising at least one ethylenic unsaturation and/or a condensable group and/or a group which is dissociable by thermal means, by photochemical means or by ionic dissociation; a self-doped electronically conductive polymer; a hydrolysable alkoxysilane; a free radical trap; a dissociating dipole; a redox couple, a complexing ligand.
 35. Ionically conductive material according to claim 33, characterized in that the substituent R_(D) of the ionic compound is an alkyl or an alkenyl which contains at least one heteroatom selected from O, N and S; an alkyl or an alkenyl carrying a hydroxy group, a carbonyl group, an amine group, a carboxyl group; an aryl, an arylalkyl, an alkylaryl or an alkenylaryl in which the lateral chains and/or the aromatic nuclei comprise heteroatoms.
 36. Material according to claim 33, characterized in that the substituent R_(D) is a recurring unit of a polymer.
 37. Ionically conductive material according to claim 33, characterized in that the substituent Z of the ionic compound is selected from the group consisting of —OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and —SC₂F₄H, —OCF═CF₂, —SCF═CF₂.
 38. Ionically conductive material according to claim 33, characterized in that the solvent is either an aprotic liquid solvent, selected from linear ethers and cyclic ethers, esters, nitrites, nitro derivatives, amides, sulfones, sulfolanes, sulfamides and partially halogenated hydrocarbons, or a polar polymer, or a mixture thereof.
 39. Ionically conductive material according to claim 38, characterized in that the solvent is a cross-linked or non-cross-linked solvating polymer, which may carry grafted ionic groups.
 40. Ionically conductive material according to claim 39, characterized in that the solvating polymer is selected from polyethers of linear structure, comb or blocks, which may form a network, based on poly (ethylene oxide), copolymers containing ethylene oxide, propylene oxide or allylglycidylether units, polyphosphazenes, cross-linked networks based on polyethylene glycol cross-linked with isocyanates, polymer networks obtained by polycondensation and carrying groups which enable the incorporation of cross-linkable groups and block copolymers in which some blocks carry functions which have redox properties.
 41. Ionically conductive material according to claim 33, characterized in that the solvent essentially consists of a liquid aprotic solvent and a polar polymer solvent comprising units containing at least one heteroatom selected from sulfur, oxygen, nitrogen and fluorine.
 42. Ionically conductive material according to claim 41, characterized in that the polar polymer mainly contains units derived from acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.
 43. Ionically conductive material according to claim 33, characterized in that it additionally contains at least one second salt.
 44. Ionically conductive material according to claim 33, characterized in that it additionally contains a mineral or organic charge in the form of powder or fibres.
 45. Electrochemical generator comprising a negative electrode and a positive electrode both separated by an electrolyte, characterized in that the electrolyte is a material according to one of claims 33 to
 44. 46. Generator according to claim 45, characterized in that the negative electrode consists of metallic lithium, or an alloy thereof, optionally in the form of nanometric dispersion in lithium oxide, or a double nitride of lithium and a transition metal, or an oxide with low potential having the general formula Li_(1+y+x/3)Ti_(2−x/3)O₄ (0≦x≦1, 0≦y≦1), or carbon and carbon products originating from pyrolysis of organic materials.
 47. Generator according to claim 45, characterized in that the positive electrode is selected from vanadium oxides VO_(x) (2≦x≦2.5), LiV₃O₈, Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x≦1; 0≦y<1), spinels of manganese Li_(y)Mn_(1−x)M_(x)O₂ (M═Cr, Al, V, Ni, 0≦x≦0,5 ; 0≦y≦2), organic polydisulfides FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, phosphates and phophosilicates of iron and lithium of olivine structure, or substituted products where iron is substituted by manganese, used alone or in admixtures.
 48. Generator according to claim 45, characterized in that the collector of the cathode is made of aluminum.
 49. Supercapacitance utilizing at least one carbon electrode with high specific surface, or an electrode containing a redox polymer, in which the electrolyte is a material according to one of claims 33 to
 44. 50. Use of a material according to one of claims 33 to 44 for p or n doping of an electronically conductive polymer.
 51. Electrochrome device in which the electrolyte is a material according to one of claims 33 to
 44. 52. Process for polymerization or cross-linking of monomers of prepolymers capable of cationic reaction, characterized in that there is used a compound according to claim 1 as photoinitiator acting as a source of acid catalyzing the reaction.
 53. Process according to claim 52, characterized in that the cation of the ionic compound is a group having a bond —N═N⁺, —N═N—, a sulfonium group, an iodonium group, or a substituted or non-substituted arene-ferrocenium cation, such group optionally being incorporated in a polymeric network.
 54. Process according to claim 52, characterized in that at least one of the substituents R_(F) or Z is a non-substituted alkyl radical or a radical comprising an oxa, sulfoxide, sulfone, phosphine oxide or phosphonate group.
 55. Process according to claim 52, characterized in that the monomers are selected from the group consisting of compounds which include a cyclic ether function, a cyclic thioether function or a cyclic amino function, vinyl compounds, vinylether, oxazolines, lactones and lactames.
 56. Process according to claim 52, characterized in that the polymer is selected from the group consisting of compounds in which epoxy groups are carried by an aliphatic chain, an aromatic chain or a heterocyclic chain.
 57. Process according to claim 52, characterized in that it consists of mixing the photoinitiator with at least one monomer or prepolymer capable of cationic polymerization, and subjecting the mixture obtained to actinic radiation, including β radiation.
 58. Process according to claim 57, characterized in that the reaction mixture is treated with radiation after having been shaped into a thin layer.
 59. Process according to claim 52, characterized in that the photoinitiator is used in the form of a solution in a solvent which is inert towards the polymerization reaction.
 60. Process according to claim 59, characterized in that the inert solvent is selected from the group consisting of acetone, methylethyl ketone, acetonitrile, propylene carbonate, y-butyrolactone, ether-esters of mono-, di-, tri- ethylene or propylene glycols, ether-alcohols of mono-, di-, tri- ethylene or propylene glycols, esters of phthalic or citric acids.
 61. Process according to claim 52, characterized in that the reaction is carried out in the presence of a solvent or a diluent consisting of a compound which is reactive towards polymerization.
 62. Process according to claim 61, characterized in that the reactive compound is selected from the group consisting of mono- and di- vinylethers of mono-, di-, tri-, tetra- ethylene or propylene glycols, trivinyl ether trimethylolpropane and divinylether of dimethanolcyclohexane, N-vinylpyrolidone, 2-propenylether of propylene carbonate.
 63. Process according to claim 52, characterized in that a photosensitizer is added to the reaction mixture.
 64. Process according to claim 63, characterized in that the photosensitizer is selected from the group consisting of anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine, tetracene, xanthone, thioxanthone, isopropylthioxantone, acetophenone, benzophenone, 1,3,5-triaryl-2-pyrazolines and derivatives thereof, in particular derivatives which are substituted on aromatic nuclei by alkyl, oxa- or aza-alkyl radicals.
 65. Process according to claim 52, characterized in that the reaction mixture additionally contains at least one monomer or prepolymer capable of free radical polymerization and a compound capable of releasing a free radical initiator under the effect of actinic radiation or D radiation or heat.
 66. Process for modifying solubility properties of a polymer having groups sensitive towards acids, characterized in that it consists of subjecting said polymer to actinic radiation or , radiation, in the presence of a compound according to claim
 1. 67. Process according to claim 65, characterized in that the polymer contains ester or arylether units derived from tertiary alcohol.
 68. Process according to claim 67, characterized in that the polymer is selected from the group consisting of homopolymers and copolymers of tertiobutyl or tertioamyl acrylate, tertiobutyl or tertioamyl itaconate, (tertiobutoxycarbonyloxystyrene) or (tertioamyloxystyrene).
 69. Process according to claim 66, characterized in that it is utilized for the chemical amplification of photoresists.
 70. Process for the polymerization of vinyl monomers, characterized in that a compound according to claim 10 is used as free radical initiator.
 71. Composition of cationic coloring material, characterized in that it contains a compound according to claim
 1. 72. Composition of cationic coloring material according to claim 71, characterized in that the negative charge(s) of the ionic group R_(F)—SO_(x)—N⁻—Z are either fixed on the molecule of the coloring material, or they constitute the counter-ion of positive charges of the coloring material.
 73. Use of a compound according to claim 1 as catalyst in Friedel and Craft reactions, Diels and Alder reactions, additions of Michael, reactions of allylation, reactions of pinacolic coupling, reactions of glycosilation, reactions of opening cycles of oxetanes, reactions of aldolization, reactions of metathesis of alkenes, polymerizations of Ziegler-Natta type, polymerizations of metathesis type by cycle opening and polymerizations of metathesis type of acyclic dienes.
 74. Use according to claim 73, characterized in that the compound is a compound according to claim 1 in which the cation is selected from lithium, magnesium, copper, zinc, tin, trivalent metals, including rare earths, platinoids, and organometallic cations.
 75. Use of a compound according to claim 6 as a solvent to carry out chemical, photochemical, electrochemical, photoelectrochemical reactions, said compound being used above its melting point.
 76. Electronically conductive material characterized in that it comprises an ionic compound according to claim
 1. 77. Electronically conductive material according to claim 76, characterized in that the cationic part of the ionic compound is a polycation consisting of a doped conjugated polymer “p”.
 78. Electronically conductive material according to claim 76, characterized in that the substituent Z of the ionic compound comprises an alkyl chain having 6 to 20 carbon atoms. 